JP2938468B2 - Multilayer ceramic capacitors - Google Patents
Multilayer ceramic capacitorsInfo
- Publication number
- JP2938468B2 JP2938468B2 JP1062415A JP6241589A JP2938468B2 JP 2938468 B2 JP2938468 B2 JP 2938468B2 JP 1062415 A JP1062415 A JP 1062415A JP 6241589 A JP6241589 A JP 6241589A JP 2938468 B2 JP2938468 B2 JP 2938468B2
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- Prior art keywords
- dielectric
- multilayer ceramic
- dielectric layer
- internal electrode
- ceramic capacitor
- Prior art date
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- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はパラジウムを含む内部電極を有する積層セラ
ミックコンデンサに関するものである。Description: TECHNICAL FIELD The present invention relates to a multilayer ceramic capacitor having an internal electrode containing palladium.
従来の技術 例えば0.11BaO−0.88TiO2−0.21Nd2O3等のBaO−TiO2
−Nd2O3系の誘電体材料を使用して誘電体層を形成し、
パラジムを内部電極とした積層セラミックコンデンサで
あった。Description of the Related Art For example 0.11BaO-0.88TiO 2 -0.21Nd 2 BaO- TiO 2 of O 3,
Forming a dielectric layer using -Nd 2 O 3 based dielectric material,
It was a multilayer ceramic capacitor using paradium as an internal electrode.
発明が解決しようとする課題 上記構造の積層セラミックコンデンサにおいては、内
部電極のデラミネーションの発生を防止するために、内
部電極を薄くする。しかしながら、Ba/（Ti＋Zr）比の
小さいものなど一般的に（TiO2＋ZrO2）を多く含む誘電
体層は焼成する際、誘電体層中に含まれる有機バインダ
ーなどにより、TiO2が還元される。そして還元により生
じたTiが内部電極のPdと化合物を作るためか、内部電極
が体積膨張し、その結果内部電極は一見玉状のようにな
り、内部電極切れを起こし、誘電体層とPdを含む内部電
極との界面の密着性が低下する。その結果、静電容量と
Ｑ値が低下し、そのバラツキが大きくなるという問題点
を有していた。Problems to be Solved by the Invention In the multilayer ceramic capacitor having the above structure, the internal electrodes are made thin in order to prevent the occurrence of delamination of the internal electrodes. However, when a dielectric layer generally containing a large amount of (TiO 2 + ZrO 2 ) such as a material having a small Ba / (Ti + Zr) ratio is fired, TiO 2 is reduced by an organic binder contained in the dielectric layer. . And because the Ti generated by the reduction forms a compound with the Pd of the internal electrode, the internal electrode expands in volume, and as a result, the internal electrode looks like a ball, causing the internal electrode to break, and the dielectric layer and Pd are separated. And the adhesiveness of the interface with the internal electrode is reduced. As a result, there has been a problem that the capacitance and the Q value decrease and the variation increases.
そこで本発明の積層セラミックコンデンサは、内部電
極切れを抑制することにより、静電容量とＱ値が大き
く、そのバラツキが小さい積層セラミックコンデンサを
提供することを目的とするものである。Therefore, an object of the multilayer ceramic capacitor of the present invention is to provide a multilayer ceramic capacitor having a large capacitance and a large Q value and a small variation by suppressing disconnection of internal electrodes.
課題を解決するための手段 この目的を達成するために、本発明の積層セラミック
コンデンサは、誘電体層と内部電極とを交互に積層した
積層体と、この積層体の前記内部電極の露出した端面に
設けた外部電極とを備え、前記誘電体層は、一般式xBaO
−ｙ｛（TiO2）(1-m)（ZrO2）ｍ｝−zRe2O3（ただし、
ｘ＋ｙ＋ｚ＝1.00,0.001≦ｍ≦0.200,Re2O3は、La2O3,P
r2O11/3,Nd2O3,Sm2O3から選ばれる少なくとも一種以上
の希土類元素の酸化物。）と表した時、x,y,zが以下の
表に示す各点a,b,c,d,e,fで囲まれるモル比の範囲から
なる主成分100重量部に対し、副成分としてV2O5を0.005
〜1.000重量部含有したものであり、前記内部電極はパ
ラジウムを含有することを特徴とするものである。Means for Solving the Problems In order to achieve this object, a multilayer ceramic capacitor according to the present invention includes a laminated body in which dielectric layers and internal electrodes are alternately laminated, and an exposed end face of the internal electrode of the laminated body. And an external electrode provided in the dielectric layer, wherein the dielectric layer has a general formula xBaO
−y ｛(TiO 2 ) (1-m) (ZrO 2 ) m ｝ −zRe 2 O 3 (However,
x + y + z = 1.00, 0.001 ≦ m ≦ 0.200, Re 2 O 3 is La 2 O 3 , P
An oxide of at least one rare earth element selected from r 2 O 11/3 , Nd 2 O 3 , and Sm 2 O 3 . ), X, y, z are the sub-components for 100 parts by weight of the main component consisting of the molar ratio range surrounded by the points a, b, c, d, e, f shown in the table below. V 2 O 5 0.005
内部 1.000 parts by weight, and the internal electrode contains palladium.
作用 この構成によると、誘電体層中の４価のTiの一部を５
価のＶで置換することによりTiO2が還元されるのを抑制
し、TiとPdとの化合物の生成を防止する。その結果、誘
電体層と内部電極の界面の密着性が向上するため、静電
容量とＱ値が大きく、そのバラツキが小さい積層セラミ
ックコンデンサとなる。 Action According to this configuration, a part of the tetravalent Ti in the dielectric layer is reduced to 5%.
Substitution with a valence V suppresses the reduction of TiO 2 and prevents the formation of a compound of Ti and Pd. As a result, the adhesion at the interface between the dielectric layer and the internal electrode is improved, so that a multilayer ceramic capacitor having a large capacitance and a large Q value and a small variation is obtained.
また従来の誘電体層は焼成により還元されたTiO2が冷
却過程である程度再酸化されるが、誘電体層の内部、及
び各結晶粒子の内側は再酸化されにくく酸素欠乏状態の
まま残る。従って酸素原子の持つ有効電荷＋2eをチタン
原子上の3d電子で中和することにより、各酸素空孔につ
いて２個のTi3+が形成され、Ti3+を介した電子ホッピン
グによって、誘電体層の絶縁抵抗、絶縁破壊強度を劣化
させる。そこで本発明は誘電体層中の４価のTiの一部を
５価のＶで置換することにより生じた陽イオン空孔で、
焼成時の酸素欠陥によるe-を補償する。その結果絶縁抵
抗、絶縁破壊強度が従来よりも向上した積層セラミック
コンデンサを得ることができる。In the conventional dielectric layer, TiO 2 reduced by firing is reoxidized to some extent during the cooling process, but the inside of the dielectric layer and the inside of each crystal grain are hardly reoxidized and remain in an oxygen-deficient state. Therefore, by neutralizing the effective charge + 2e of the oxygen atom with 3d electrons on the titanium atom, two Ti 3+ are formed for each oxygen vacancy, and electron hopping via the Ti 3+ causes the dielectric layer Degrades insulation resistance and dielectric breakdown strength. Therefore, the present invention provides a cation vacancy generated by substituting a part of tetravalent Ti in the dielectric layer with pentavalent V,
Due to oxygen defect during firing e - to compensate for. As a result, it is possible to obtain a multilayer ceramic capacitor having improved insulation resistance and dielectric breakdown strength as compared with conventional ones.
実施例 以下に、本発明を具体的実施例により説明する。EXAMPLES Hereinafter, the present invention will be described with reference to specific examples.
（実施例１） 出発原料には化学的に高純度のBaCO3,TiO2,ZrO2,La2O
3,Pr6O11,Nd2O5,Sm2O3およびV2O5粉末を下記の第１表に
示す組成比になるように秤量し、めのうボールを備えた
ゴム内張りのボールミルに純水とともに入れ、湿式混合
後、脱水乾燥した。この乾燥粉末を高アルミナ質のルツ
ボに入れ、空気中で1100℃にて２時間仮焼した。この仮
焼粉末をめのうボールを備えたゴム内張りのボールミル
に純水とともに入れ、湿式粉砕後、脱水乾燥した。この
粉砕粉末に、有機バインダーを加え、均質とした後、32
メッシュのふるいを通して整粒し、金型と油圧プレスを
用いて成形圧力1ton/cm2で、直径15mm、厚み0.4mmに成
形した。次いで成形円板をジルコニア粉末を敷いたアル
ミナ質のサヤに入れ、空気中にて下記の第１表に示す組
成比の誘電体磁器を得た。このようにして得られた誘電
体磁器円板は、厚みと直径を測定し、誘電率、良好度
Ｑ、静電容量温度係数測定用試料は、誘電体磁器円板の
両面全体に銀電極を焼き付け、絶縁抵抗、絶縁破壊強度
測定用試料は、誘電体磁器円板の外周より内側に1mmの
幅で銀電極のない部分を設け、銀電極を焼き付けた。そ
して誘電率、良好度Ｑ、静電容量温度係数はYHP社製デ
ジタルLCRメータのモデル4275Aを使用し、測定温度20
℃、測定電圧1.0Vrms、測定周波数1MHzでの測定より求
めた。なお、静電容量温度係数は、20℃と85℃の静電容
量を用いて、次式により求めた。(Example 1) As starting materials, chemically pure BaCO 3 , TiO 2 , ZrO 2 , La 2 O
3 , Pr 6 O 11 , Nd 2 O 5 , Sm 2 O 3 and V 2 O 5 powders are weighed so as to have the composition ratios shown in Table 1 below, and purified in a rubber-lined ball mill equipped with an agate ball. It was put together with water, wet-mixed, and dehydrated and dried. The dried powder was placed in a high alumina crucible and calcined in air at 1100 ° C. for 2 hours. The calcined powder was put together with pure water into a rubber-lined ball mill equipped with an agate ball, wet pulverized, and then dehydrated and dried. An organic binder was added to the pulverized powder to make it homogenous.
The mixture was sized through a mesh sieve and formed into a diameter of 15 mm and a thickness of 0.4 mm using a mold and a hydraulic press at a forming pressure of 1 ton / cm 2 . Next, the molded disk was placed in an alumina sheath covered with zirconia powder, and a dielectric ceramic having a composition ratio shown in Table 1 below was obtained in air. The dielectric porcelain disk thus obtained was measured for thickness and diameter, and the dielectric constant, goodness Q and capacitance temperature coefficient measurement sample were provided with silver electrodes on both surfaces of the dielectric porcelain disk. For the sample for measurement of baking, insulation resistance, and dielectric strength, a portion having no silver electrode with a width of 1 mm was provided inside the outer periphery of the dielectric porcelain disk, and the silver electrode was baked. The dielectric constant, goodness Q, and capacitance temperature coefficient were measured using a digital LCR meter model 4275A manufactured by YHP.
° C, a measurement voltage of 1.0 Vrms, and a measurement frequency of 1 MHz. The capacitance temperature coefficient was obtained by the following equation using the capacitances at 20 ° C. and 85 ° C.
TC＝（Ｃ−C0）/C0×1/65×106 TC:静電容量温度係数（ppm/℃） C0:20℃での静電容量（pF） C:85℃での静電容量（pF） また、誘電率は次式より求めた。TC = (C−C 0 ) / C 0 × 1/65 × 10 6 TC: Capacitance temperature coefficient (ppm / ° C) C 0 : Capacitance at 20 ° C (pF) C: Static at 85 ° C Capacitance (pF) The dielectric constant was determined by the following equation.
Ｋ＝143.8×C0×t/D2 K:誘電率 C0:20℃での静電容量（pF） D:誘電体磁器の直径（mm） t:誘電体磁器の厚み（mm） さらに、絶縁抵抗は、YHP社製HRメータのモデル4329A
を使用し、測定電圧50V.D.C.、測定時間１分間による測
定により求めた。K = 143.8 × C 0 × t / D 2 K: dielectric constant C 0 : capacitance at 20 ° C. (pF) D: diameter of dielectric ceramic (mm) t: thickness of dielectric ceramic (mm) Insulation resistance is YHP HR meter model 4329A
And a measurement voltage of 50 V DC for a measurement time of 1 minute.
そして、絶縁破壊強度は、菊水電子工業（株）製高電
圧電源PHS35K−３形を使用し、試料をシリコンオイル中
に入れ、昇圧速度50V/secにより求めた絶縁破壊電圧を
誘電体厚みで除算し、1mm当たりの絶縁破壊強度とし
た。また、結晶粒径は、倍率400での光学顕微鏡観察に
より求めた。The dielectric breakdown strength was measured by using a high voltage power supply PHS35K-3 manufactured by Kikusui Electronics Co., Ltd., placing the sample in silicon oil, and dividing the dielectric breakdown voltage obtained at a step-up speed of 50 V / sec by the dielectric thickness. And the dielectric breakdown strength per 1 mm. Further, the crystal grain size was determined by observation with an optical microscope at a magnification of 400.
試験条件を第１表に併せて示し、試験結果を下記の第
２表に示す。The test conditions are shown in Table 1, and the test results are shown in Table 2 below.
ここで第１図は誘電体層の主成分の組成範囲を示す三
元図であり、主成分の組成範囲を限定した理由を第１図
を参照しながら説明する。すなわち、Ａ領域では焼結が
著しく困難である。また、Ｂ領域では良好度Ｑが低下
し、実用的でなくなる。さらに、C,D領域では静電容量
温度係数がマイナス側に大きくなりすぎて実用的でなく
なる。そして、Ｅ領域では静電容量温度係数がプラス方
向に移行するが、誘電率が小さく実用的でなくなる。ま
た、Re2O3をLa2O3,Pr2O11/3,Nd2O3,Sm2O3から選ぶこと
により、La2O3,Pr2O11/3,Nd2O3,Sm2O3の順で誘電率を大
きく下げることなく、静電容量温度係数をプラス方向に
移行することが可能であり、La2O3,Pr2O11/3,Nd2O3,Sm2
O3の一種あるいは組み合わせにより静電容量温度係数の
調整が可能である。 Here, FIG. 1 is a ternary diagram showing the composition range of the main component of the dielectric layer, and the reason for limiting the composition range of the main component will be described with reference to FIG. That is, sintering is extremely difficult in the region A. Further, in the region B, the degree of goodness Q is reduced, and is not practical. Furthermore, in the C and D regions, the temperature coefficient of capacitance becomes too large on the minus side, which is not practical. Then, in the E region, the capacitance temperature coefficient shifts in the positive direction, but the dielectric constant is too small to be practical. Also, by selecting Re 2 O 3 from La 2 O 3 , Pr 2 O 11/3 , Nd 2 O 3 , Sm 2 O 3 , La 2 O 3 , Pr 2 O 11/3 , Nd 2 O 3 , Without significantly lowering the dielectric constant in the order of Sm 2 O 3 , it is possible to shift the temperature coefficient of capacitance in the positive direction, La 2 O 3 , Pr 2 O 11/3 , Nd 2 O 3 , Sm Two
The capacitance temperature coefficient can be adjusted by one or a combination of O 3 .
また、TiO2をZrO2で置換することにより、誘電率、良
好度Ｑ、静電容量温度係数、絶縁抵抗の値を大きく変え
ることなく、結晶粒径を小さくし、絶縁破壊強度を大き
くする効果を有し、その置換率ｍが0.001未満では置換
効果がなく、一方0.200を越えると誘電率、良好度Ｑ、
絶縁抵抗が低下する。In addition, by replacing TiO 2 with ZrO 2 , the effect of reducing the crystal grain size and increasing the dielectric breakdown strength without greatly changing the values of dielectric constant, goodness Q, capacitance temperature coefficient, and insulation resistance. When the substitution rate m is less than 0.001, there is no substitution effect, while when it exceeds 0.200, the dielectric constant, the degree of goodness Q,
Insulation resistance decreases.
（実施例２） 出発原料には化学的に高純度のBaCO3,TiO2,ZrO2,La2O
3,Pr6O11,Nd2O5,Sm2O3,V2O5,MnO2,ZnO,Fe2O3およびSiO2
粉末を第３表に示す組成比になるように秤量し、それ以
降は実施例１の場合と同様に処理して第３表に示す組成
比の誘電体磁器を得た。(Example 2) As starting materials, chemically pure BaCO 3 , TiO 2 , ZrO 2 , La 2 O
3 , Pr 6 O 11 , Nd 2 O 5 , Sm 2 O 3 , V 2 O 5 , MnO 2 , ZnO, Fe 2 O 3 and SiO 2
The powder was weighed so as to have the composition ratio shown in Table 3, and thereafter the same treatment as in Example 1 was performed to obtain a dielectric ceramic having the composition ratio shown in Table 3.
これらの試料の試験方法は、実施例１と同様であり、
試験条件を第３表に併せて示し、試験結果を下記の第４
表に示す。The test method for these samples is the same as in Example 1,
The test conditions are shown in Table 3 and the test results are shown in Table 4 below.
It is shown in the table.
このようにマンガン、亜鉛、鉄及びケイ素の酸化物か
ら選ばれる少なくとも一種以上をそれぞれMnO2,ZnO,Fe2
O3及びSiO2に換算して0.05〜1.00重量部添加することに
より、誘電体磁器の焼結性を向上させることができる。
その添加量が0.05重量部未満では添加効果がなく、一方
1.00重量部を越えると誘電率が低下し実用的でなくな
る。 Thus, at least one selected from manganese, zinc, iron and oxides of silicon is MnO 2 , ZnO, Fe 2
By adding 0.05 to 1.00 parts by weight in terms of O 3 and SiO 2 , the sinterability of the dielectric ceramic can be improved.
If the addition amount is less than 0.05 parts by weight, there is no effect of addition, while
If it exceeds 1.00 parts by weight, the dielectric constant is lowered, and it is not practical.
（実施例３） 出発原料には化学的に高純度のBaCO3,TiO2,ZrO2,La2O
3,Pr6O11,Nd2O5,Sm2O3およびV2O5粉末を使用し、主成分
0.11BaO−0.68｛（TiO2）0.9（ZrO2）0.1｝−0.21Nd2O3
に対し、V2O5を0,0.001,0.005,0.010,0.100,1.000,2.00
0wt％含有した仮焼粉を実施例１と同様の方法で作製す
る。ただし、V2O5の含有量が0,0.001,2.000wt％は本発
明の範囲外であり、0.005,0.010,0.100,1.000wt％は本
発明の範囲内である。(Example 3) As starting materials, chemically pure BaCO 3 , TiO 2 , ZrO 2 , La 2 O
3, Pr 6 O 11, Nd 2 O 5, Sm 2 O 3 and V 2 O 5 powder using principal component
0.11BaO−0.68 ｛(TiO 2 ) 0.9 (ZrO 2 ) 0.1 ｝ −0.21Nd 2 O 3
In contrast, V 2 O 5 is 0,0.001,0.005,0.010,0.100,1.000,2.00
A calcined powder containing 0 wt% is produced in the same manner as in Example 1. However, the content of V 2 O 5 of 0,0.001,2.000 wt% is out of the range of the present invention, and 0.005,0.010,0.100,1.000 wt% is within the range of the present invention.
この仮焼粉砕粉末に、有機バインダー、可塑剤、分散
剤、有機溶剤を加え、アルミナボールを備えたポリエチ
レン製ポットで混合し、スラリーを作製した。混合後、
300メッシュのナイロン布を使用し、ろ過した。ろ過後
のスラリーは、ドクターブレードにより、焼結後の誘電
体厚みが12μｍとなるように、離型処理をしたポリエス
テルフィルム上にシートを成形した。An organic binder, a plasticizer, a dispersant, and an organic solvent were added to the calcined and pulverized powder, and mixed with a polyethylene pot equipped with alumina balls to prepare a slurry. After mixing
Filtration was performed using a 300 mesh nylon cloth. The slurry after filtration was formed into a sheet on a polyester film that had been subjected to a mold release treatment by a doctor blade so that the dielectric thickness after sintering was 12 μm.
次に、ポリエステルフィルムから剥がしたシート10枚
を支持台の上に積層した。この上に、昭栄化学（株）製
内部電極パラジウムペーストML−3724を焼結後の内部電
極厚みが２μｍとなるようにスクリーン印刷し、乾燥し
た。この上にポリエステルフィルムから剥がしたシート
１枚を積層した。この上に、焼結後の内部電極重なり寸
法が1.2mm×0.7mmとなるように印刷位置をずらして内部
電極パラジウムペーストを印刷し、乾燥後、ポリエステ
ルフィルムから剥がしたシート１枚を積層した。これら
の操作を、誘電体層数が19となるまで繰り返した。この
上に、ポリエステルフィルムから剥がしたシート10枚を
積層した。この積層体を焼結後、内部電極重なり寸法が
1.2mm×0.7mm、誘電体厚みが12μｍ、誘電体層数が19の
積層構造を持つ積層セラミックコンデンサとなるように
切断した。この切断した試料は、ジルコニア粉末を敷い
たアルミナ質のサヤに入れ、空気中にて室温から350℃
までを５℃/hrで昇温し、350℃より100℃/hrで昇温し、
1270℃で２時間焼成後、100℃/hrで室温まで降温した。
次いで、焼成後の試料は、耐水サンドペーパーを内側に
貼ったポリエチレンポットに純水と共に入れ、ポリエチ
レンポットを回転させ焼成後の試料面を研磨し、外部電
極と接合する内部電極部分を充分露出させた。この試料
はポリエチレンポットより取り出し乾燥後、内部電極露
出部分に銀の外部電極を焼き付け、内部電極と導通さ
せ、積層セラミックコンデンサを作製した。Next, ten sheets peeled from the polyester film were laminated on a support. On this, an internal electrode palladium paste ML-3724 manufactured by Shoei Chemical Co., Ltd. was screen-printed such that the internal electrode thickness after sintering became 2 μm, and dried. One sheet peeled from the polyester film was laminated thereon. On this, the printing position was shifted so that the internal electrode overlapping dimension after sintering was 1.2 mm × 0.7 mm, the internal electrode palladium paste was printed, and after drying, one sheet peeled off from the polyester film was laminated. These operations were repeated until the number of dielectric layers reached 19. On this, 10 sheets peeled from the polyester film were laminated. After sintering this laminate, the internal electrode overlap dimension
The multilayer ceramic capacitor was cut into a laminated ceramic capacitor having a laminated structure of 1.2 mm × 0.7 mm, a dielectric thickness of 12 μm, and 19 dielectric layers. The cut sample is placed in an alumina sheath covered with zirconia powder, and is heated from room temperature to 350 ° C. in air.
Up to 5 ° C / hr, from 350 ° C at 100 ° C / hr,
After firing at 1270 ° C for 2 hours, the temperature was lowered to room temperature at 100 ° C / hr.
Next, the fired sample is put together with pure water into a polyethylene pot with a waterproof sandpaper stuck on the inside, and the polyethylene pot is rotated to polish the fired sample surface to sufficiently expose the internal electrode portion to be joined to the external electrode. Was. This sample was taken out of the polyethylene pot and dried, and then a silver external electrode was baked on the exposed portion of the internal electrode to make conduction with the internal electrode, thereby producing a multilayer ceramic capacitor.
これらの試料の静電容量、良好度Ｑ、静電容量温度係
数、絶縁抵抗、絶縁破壊強度は実施例１と同様の条件で
測定により求めた。また、積層構造の確認は、積層セラ
ミックコンデンサの長さ方向および幅方向の約1/2を研
磨断面を、内部電極の重なり寸法は倍率100、誘電体厚
みと内部電極厚みは倍率400での光学顕微鏡観察により
求めた。The capacitance, goodness Q, capacitance temperature coefficient, insulation resistance, and dielectric breakdown strength of these samples were determined by measurement under the same conditions as in Example 1. In addition, the confirmation of the laminated structure was performed by polishing about 断面 of the length and width directions of the multilayer ceramic capacitor in a polished cross section, the overlap size of the internal electrodes was 100, and the dielectric thickness and internal electrode thickness were 400 magnifications. It was determined by microscopic observation.
この測定結果を第２図に示す。この第２図を用いて誘
電体層中の副成分V2O5の含有範囲を限定した理由をグラ
フで説明する。第２図に示すようにV2O5を含有すること
により、絶縁抵抗、絶縁破壊強度が向上し、また静電容
量と良好度Ｑを高め、静電容量と良好度Ｑのバラツキを
小さくする効果を有する。そして、V2O5の含有により、
絶縁抵抗、絶縁破壊強度は向上するが、V2O5の含有量が
主成分100重量部に対し、0.005重量部未満は静電容量と
良好度Ｑが低く、また、静電容量と良好度Ｑのバラツキ
が大きいため、本発明の範囲から除外した。一方、V2O5
の含有量が主成分に対し、1.000重量部を越えると良好
度Ｑ、絶縁抵抗が低下し、静電容量温度係数がマイナス
側に大きくなり実用的でなくなる。FIG. 2 shows the measurement results. The reason why the content range of the subcomponent V 2 O 5 in the dielectric layer is limited will be described with reference to FIG. 2 using a graph. As shown in FIG. 2, by containing V 2 O 5 , the insulation resistance and the dielectric breakdown strength are improved, the capacitance and the goodness Q are increased, and the variation between the capacitance and the goodness Q is reduced. Has an effect. And, due to the inclusion of V 2 O 5 ,
Although the insulation resistance and dielectric breakdown strength are improved, when the content of V 2 O 5 is less than 0.005 parts by weight with respect to 100 parts by weight of the main component, the capacitance and the goodness Q are low, and the capacitance and the goodness are low. Since the variation of Q was large, it was excluded from the scope of the present invention. On the other hand, V 2 O 5
If the content exceeds 1.000 parts by weight with respect to the main component, the degree of goodness Q and the insulation resistance decrease, and the temperature coefficient of capacitance increases to the minus side, which is not practical.
なお、実施例における誘電体磁器及び積層セラミック
コンデンサの作製方法では、BaCO3,TiO2,ZrO2,La2O3,Pr
6O11,Nd2O5,Sm2O3,V2O5,MnO2,ZnO,Fe2O3およびSiO2を使
用したが、この方法に限定されるものではなく、所望の
組成比になるようにBaTiO3などの化合物、あるいは炭酸
塩、水酸化物など空気中での加熱により、BaO,TiO2,ZrO
2,La2O3,Pr6O11,Nd2O5,Sm2O3,V2O5,MnO2,ZnO,Fe2O3およ
びSiO2となる化合物を使用しても実施例と同程度の特性
を得ることができる。In the method of manufacturing the dielectric porcelain and the multilayer ceramic capacitor in Examples, BaCO 3 , TiO 2 , ZrO 2 , La 2 O 3 , Pr
6 O 11 , Nd 2 O 5 , Sm 2 O 3 , V 2 O 5 , MnO 2 , ZnO, Fe 2 O 3 and SiO 2 were used, but it is not limited to this method, and the desired composition ratio BaO, TiO 2 , ZrO by heating in air such as BaTiO 3 or carbonate, hydroxide, etc.
2 , La 2 O 3 , Pr 6 O 11 , Nd 2 O 5 , Sm 2 O 3 , V 2 O 5 , MnO 2 , ZnO, Fe 2 O 3 and SiO 2 Similar characteristics can be obtained.
また、主成分をあらかじめ仮焼し、副成分を添加して
も実施例と同程度の特性を得ることができる。Further, even if the main component is calcined in advance and the subcomponent is added, the same characteristics as those of the embodiment can be obtained.
発明の効果 以上、本発明によると、誘電体層中の４価のTiの一部
を５価のＶで置換することにより生じた陽イオン空孔
で、焼成時の酸素欠陥によるe-を補償し、TiO2が還元さ
れるのを抑制するため、TiとPdとの化合物の生成を防止
できる。その結果、誘電体層と内部電極の界面の密着性
が向上するため、静電容量とＱ値が大きく、そのバラツ
キが小さい積層セラミックコンデンサを得ることができ
る。As described above, according to the present invention, cation vacancies generated by substituting a part of tetravalent Ti in a dielectric layer with pentavalent V compensate for e − due to oxygen defects during firing. However, since the reduction of TiO 2 is suppressed, the formation of a compound of Ti and Pd can be prevented. As a result, the adhesion at the interface between the dielectric layer and the internal electrode is improved, so that a multilayer ceramic capacitor having a large capacitance and a large Q value and a small variation can be obtained.
また従来の誘電体層は焼成時に還元されたTiO2が冷却
過程である程度再酸化されるが、誘電体層の内部、及び
各結晶粒子の内側は再酸化されにくく酸素欠乏状態のま
ま残る。この酸素欠乏が電気伝導に寄与し、誘電体層の
絶縁抵抗、絶縁破壊強度を劣化させる。本発明の誘電体
層は、４価のTiの一部を５価のＶで置換することにより
生じた陽イオン空孔で、焼成時の酸素欠陥によるe-を補
償する。従って絶縁抵抗、絶縁破壊強度が従来よりも向
上した積層セラミックコンデンサを得ることができる。Further, in the conventional dielectric layer, TiO 2 reduced during firing is reoxidized to some extent during the cooling process, but the inside of the dielectric layer and the inside of each crystal particle are hardly reoxidized and remain in an oxygen-deficient state. This oxygen deficiency contributes to electric conduction and degrades the insulation resistance and dielectric breakdown strength of the dielectric layer. The dielectric layer of the present invention compensates for e − due to oxygen vacancies during firing, by cation vacancies generated by substituting a part of tetravalent Ti with pentavalent V. Therefore, it is possible to obtain a multilayer ceramic capacitor having improved insulation resistance and dielectric breakdown strength as compared with the prior art.
第１図は本発明にかかる誘電体層の主成分の組成範囲を
説明する三元図、第２図は本発明に係る誘電体層の主成
分0.11BaO−0.63｛（TiO2）0.9（ZrO2）0.1｝−0.21Nd2
O3に対する副成分V2O5の含有効果を、誘電体厚み:12μ
ｍ、内部電極重なり寸法:1.2mm×0.7mm、誘電体層数:19
の積層構造をもつ積層セラミックコンデンサの電気特性
で示すグラフである。FIG. 1 is a ternary diagram for explaining the composition range of the main component of the dielectric layer according to the present invention, and FIG. 2 is the ternary diagram of the main component of the dielectric layer according to the present invention, 0.11BaO−0.63 ｛(TiO 2 ) 0.9 (ZrO). 2 ) 0.1 ｝ −0.21Nd 2
The effect of the inclusion of subcomponent V 2 O 5 on O 3 is shown by dielectric thickness: 12 μ
m, internal electrode overlap dimensions: 1.2 mm x 0.7 mm, number of dielectric layers: 19
5 is a graph showing electrical characteristics of the multilayer ceramic capacitor having the multilayer structure of FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 悟司 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 木村 猛 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭62−83364（ＪＰ，Ａ) 特開 昭49−59299（ＪＰ，Ａ) 特開 昭63−246810（ＪＰ，Ａ) 特開 昭63−298910（ＪＰ，Ａ) 特開 昭63−292509（ＪＰ，Ａ) 「工業材料」1985年４月号（第33巻. 第４号）ｐ．39−48 「ニューケラス３ 積層セラミックコ ンデンサ」1988年９月26日（株）学献社 発行 Ｐ．19〜25 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Satoshi Endo 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-62-83364 (JP, A) JP-A-49-59299 (JP, A) JP-A-63-246810 (JP, A) JP-A-63-298910 (JP, A) JP-A-63-292509 (JP, A) "Industrial Materials", April 1985, Vol. 33, No. 4, p. 39-48 "New Keras 3 Multilayer Ceramic Capacitor" Published by Gakudensha Co., Ltd. on September 26, 1988. 19-25
Claims (2)
層体と、この積層体の前記内部電極の露出した端面に設
けた外部電極とを備え、前記誘電体層は、一般式xBaO−
ｙ｛（TiO2）(1-m)（ZrO2）ｍ｝−zRe2O3（ただし、ｘ
＋ｙ＋ｚ＝1.00、0.001≦ｍ≦0.200、Re2O3は、La2O3,P
r2O11/3,Nd2O3,Sm2O3から選ばれる少なくとも一種類以
上の希土類元素の酸化物。）と表した時、x,y,zが以下
の表に示す各点a,b,c,d,e,fで囲まれるモル比の範囲か
らなる主成分100重量部に対し、副成分としてV2O5を0.0
05〜1.000重量部含有したものであり、前記内部電極
は、パラジウムを含有することを特徴とする積層セラミ
ックコンデンサ。 1. A laminate comprising alternately laminated dielectric layers and internal electrodes, and an external electrode provided on an exposed end face of the internal electrode of the laminate, wherein the dielectric layer has a general formula xBaO −
y ｛(TiO 2 ) (1-m) (ZrO 2 ) m ｝ -zRe 2 O 3 (where x
+ Y + z = 1.00, 0.001 ≦ m ≦ 0.200, Re 2 O 3 is La 2 O 3 , P
An oxide of at least one or more rare earth elements selected from r 2 O 11/3 , Nd 2 O 3 , and Sm 2 O 3 . ), X, y, z are the sub-components for 100 parts by weight of the main component consisting of the molar ratio range surrounded by the points a, b, c, d, e, f shown in the table below. V 2 O 5 to 0.0
Wherein the internal electrode contains palladium.
100重量部に対して、さらにマンガン、亜鉛、鉄、及び
ケイ素の酸化物の中から選ばれる少なくとも一種類以上
をそれぞれMnO2,ZnO,Fe2O3及びSiO2に換算して0.05〜1.
00重量部含有させたことを特徴とする特許請求の範囲第
１項に記載の積層セラミックコンデンサ。2. A combination of a main component and a sub-component of a dielectric layer.
Per 100 parts by weight, more manganese, zinc, iron, and at least one or more, respectively MnO 2, ZnO selected from the oxides of silicon, in terms of Fe 2 O 3 and SiO 2 0.05 to 1.
2. The multilayer ceramic capacitor according to claim 1, wherein said multilayer ceramic capacitor is contained by 00 parts by weight.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1062415A JP2938468B2 (en) | 1989-03-15 | 1989-03-15 | Multilayer ceramic capacitors |
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| Publication Number | Publication Date |
|---|---|
| JPH02242522A JPH02242522A (en) | 1990-09-26 |
| JP2938468B2 true JP2938468B2 (en) | 1999-08-23 |
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ID=13199497
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|---|---|---|---|
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| JP2000143341A (en) * | 1998-09-11 | 2000-05-23 | Murata Mfg Co Ltd | Dielectric ceramic composition and multilayer ceramic part |
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|---|---|---|---|---|
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-
1989
- 1989-03-15 JP JP1062415A patent/JP2938468B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 「ニューケラス３ 積層セラミックコンデンサ」１９８８年９月２６日（株）学献社発行 Ｐ．１９〜２５ |
| 「工業材料」１９８５年４月号（第３３巻．第４号）ｐ．３９−４８ |
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