JP3142014B2 - Manufacturing method of multilayer ceramic capacitor - Google Patents
Manufacturing method of multilayer ceramic capacitorInfo
- Publication number
- JP3142014B2 JP3142014B2 JP03239397A JP23939791A JP3142014B2 JP 3142014 B2 JP3142014 B2 JP 3142014B2 JP 03239397 A JP03239397 A JP 03239397A JP 23939791 A JP23939791 A JP 23939791A JP 3142014 B2 JP3142014 B2 JP 3142014B2
- Authority
- JP
- Japan
- Prior art keywords
- dielectric
- internal electrode
- copper
- ceramic capacitor
- multilayer ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003985 ceramic capacitor Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- 239000005751 Copper oxide Substances 0.000 description 10
- 229910000431 copper oxide Inorganic materials 0.000 description 10
- 238000010304 firing Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000002003 electrode paste Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、内部電極とセラミック
グリーンシートを重ね合わせて一体焼成する積層セラミ
ックコンデンサの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a laminated ceramic capacitor in which internal electrodes and ceramic green sheets are superposed and integrally fired.
【０００２】[0002]
【従来の技術】通常、積層セラミックコンデンサは、誘
電体セラミックと内部電極とを所定枚数互いに積層し、
両端部に一対の外部電極を設けた構成を有している。上
下に対向する内部電極間に静電容量が発生し、この静電
容量は外部電極から取り出される。2. Description of the Related Art In general, a multilayer ceramic capacitor is formed by laminating a predetermined number of dielectric ceramics and internal electrodes together.
It has a configuration in which a pair of external electrodes are provided at both ends. Capacitance is generated between the upper and lower internal electrodes, and this capacitance is taken out from the external electrodes.
【０００３】このような積層セラミックコンデンサの製
造工程において、誘電体材料として従来から用いられて
きたチタン酸バリウム系のセラミックは、１２５０〜１
４００℃の焼成温度が必要であった。そのため、この誘
電体材料を用いた積層セラミックコンデンサの内部電極
には、誘電体セラミックが焼結する温度以上の融点を持
った白金、パラジウム等の高価な貴金属を用いざるを得
なかった。In the manufacturing process of such a multilayer ceramic capacitor, barium titanate-based ceramics conventionally used as a dielectric material are 1250-1.
A firing temperature of 400 ° C. was required. For this reason, expensive noble metals such as platinum and palladium having a melting point higher than the temperature at which the dielectric ceramic is sintered have to be used for the internal electrodes of the multilayer ceramic capacitor using this dielectric material.
【０００４】しかし、最近では、小型でありながら大容
量を有し、かつ、内部電極にかかるコストを下げるた
め、チタン酸バリウム系よりも誘電率が高く、また、１
０００℃以下の低温で焼成可能である鉛複合ペロブスカ
イトを主成分とする、いわゆる鉛系の誘電体材料を用い
ると共に、内部電極に銅あるいは銅合金を用いた積層セ
ラミックコンデンサが提案されている。However, recently, in order to reduce the cost of the internal electrode while having a small capacity, the dielectric constant is higher than that of barium titanate.
A multilayer ceramic capacitor using a so-called lead-based dielectric material mainly composed of a lead composite perovskite that can be fired at a low temperature of 000 ° C. or less and using copper or a copper alloy for an internal electrode has been proposed.
【０００５】さらに、銅は、一般に１０００℃程度の低
温焼成の積層セラミックコンデンサの内部電極として用
いられる銀／パラジウム合金に比べて電気抵抗が低いた
め、これを内部電極に用いることにより、等価直列抵抗
の低い積層セラミックコンデンサを得ることができる。
一方、製造方法の面では、内部電極は、一般に前記金属
をペースト化したものを、所定のパターンにスクリーン
印刷することにより形成されてきた。Further, since copper has a lower electric resistance than a silver / palladium alloy generally used as an internal electrode of a multilayer ceramic capacitor fired at a low temperature of about 1000 ° C., an equivalent series resistance is obtained by using this for the internal electrode. , A multilayer ceramic capacitor having a low value of
On the other hand, in terms of the manufacturing method, the internal electrodes have generally been formed by screen-printing a paste of the metal in a predetermined pattern.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、金属ペ
ーストの原料として銅を用いた場合、脱バインダー工程
をバインダーの分解が進むような高酸素分圧下で行う
と、銅が酸化膨張するため、特にデラミネーションやク
ラックを生じやすい。この酸化膨張の際に誘電体セラミ
ックに与える応力の大きさは、誘電体セラミックの厚み
に対して内部電極の厚みが大きい場合に特に問題とな
る。However, when copper is used as a raw material of the metal paste, copper is oxidized and expanded when the debinding step is performed under a high oxygen partial pressure at which the decomposition of the binder proceeds. Lamination and cracks are likely to occur. The magnitude of the stress applied to the dielectric ceramic during the oxidative expansion is particularly problematic when the thickness of the internal electrode is larger than the thickness of the dielectric ceramic.
【０００７】そこで、内部電極パターンの印刷を酸化銅
を原料としたペーストを用いて行い、脱バインダー時に
内部電極の酸化膨張が起こらないようにする方法が提案
されている。この場合、脱バインダー後に、内部電極を
酸化銅から金属銅に還元することが必要になるが、その
処理が不十分であると、内部電極の一部が酸化銅のまま
残り、それが焼成中に誘電体セラミックに拡散して、誘
電体セラミックの絶縁抵抗を低くすることになる。即
ち、誘電体セラミックをできるだけ還元させず、内部電
極のみ還元させようとするとこのような問題が起こりや
すい。Therefore, a method has been proposed in which the internal electrode pattern is printed using a paste made of copper oxide as a raw material so that the internal electrode does not undergo oxidative expansion during binder removal. In this case, it is necessary to reduce the internal electrode from copper oxide to metallic copper after debinding, but if the treatment is insufficient, part of the internal electrode remains as copper oxide, which is being burned. Then, the dielectric ceramic diffuses into the dielectric ceramic to lower the insulation resistance of the dielectric ceramic. In other words, such a problem is likely to occur when it is attempted to reduce only the internal electrode without reducing the dielectric ceramic as much as possible.
【０００８】本発明は、このような状況に鑑みてなされ
たもので、銅あるいは銅合金を内部電極とし、かつ誘電
体セラミック層の厚みが薄くなっても前述の問題点が発
生することのない積層セラミックコンデンサの製造方法
を提供するものである。The present invention has been made in view of such circumstances, and the above-described problems do not occur even when copper or a copper alloy is used as an internal electrode and the thickness of the dielectric ceramic layer is reduced. An object of the present invention is to provide a method for manufacturing a multilayer ceramic capacitor.
【０００９】[0009]
【課題を解決するための手段】以上の課題を解決するた
め、本発明の要旨とするところは、銅あるいは銅合金を
内部電極とする積層セラミックコンデンサの製造方法に
おいて、バインダー成分を除去した後に誘電体と内部電
極を共に還元させ、その後、内部電極が酸化せず、誘電
体が酸化する雰囲気中で前記誘電体と内部電極を焼成す
ることを特徴とする。SUMMARY OF THE INVENTION In order to solve the above problems, the gist of the present invention is to provide a method of manufacturing a multilayer ceramic capacitor using copper or a copper alloy as an internal electrode, after removing a binder component and removing a dielectric component. The method is characterized in that both the body and the internal electrode are reduced, and thereafter, the dielectric and the internal electrode are fired in an atmosphere in which the internal electrode is not oxidized and the dielectric is oxidized.
【００１０】[0010]
【作用】以上の製造方法において、生ユニット状態の内
部電極材料として酸化銅を含んでいても、脱バインダー
時に内部電極の酸化膨張が起こらず、誘電体セラミック
を薄層化してもデラミネーションやクラックの発生を抑
えることができる。初期状態が酸化銅である内部電極を
用いる際には、脱バインダー後に内部電極の還元処理が
必要になるが、本発明では従来方法と異なり誘電体をも
還元してしまうような強還元条件で内部電極の還元処理
を行うため、銅−酸化銅、鉛−酸化鉛の平衡酸素分圧か
ら考えて、酸化銅は完全に金属銅に還元される。In the above manufacturing method, even if copper oxide is contained as an internal electrode material in a raw unit state, oxidative expansion of the internal electrode does not occur at the time of debinding, and delamination or cracking occurs even when the dielectric ceramic is made thin. Can be suppressed. When using an internal electrode whose initial state is copper oxide, a reduction treatment of the internal electrode is required after debinding, but in the present invention, unlike the conventional method, under a strong reducing condition that the dielectric is also reduced. In order to reduce the internal electrode, the copper oxide is completely reduced to metallic copper in view of the equilibrium oxygen partial pressure of copper-copper oxide and lead-lead oxide.
【００１１】ここで、焼成中の内部電極からの銅の拡散
は、その蒸気圧等から考えて酸化銅の状態での気相拡散
と液相拡散によると考えられ、前記還元処理を行うこと
によって、内部電極からの銅の拡散を抑えることができ
る。銅を内部電極とする積層セラミックコンデンサの誘
電体の絶縁抵抗の低下は、この酸化銅の拡散が原因とな
っているため、本製造方法の如く酸化銅の拡散を抑える
ことで、誘電体の絶縁抵抗の低下は起こらない。Here, diffusion of copper from the internal electrode during firing is considered to be due to gas phase diffusion and liquid phase diffusion in the state of copper oxide in view of the vapor pressure and the like. In addition, diffusion of copper from the internal electrodes can be suppressed. Since the diffusion of copper oxide is the cause of the decrease in the insulation resistance of the dielectric of the multilayer ceramic capacitor having copper as an internal electrode, the diffusion of copper oxide is suppressed as in the present manufacturing method, and the insulation of the dielectric is reduced. No reduction in resistance occurs.
【００１２】また、本製造方法では還元処理後に誘電体
の再酸化処理を行うことで、誘電体セラミックの焼成過
程における、誘電体の還元により生成した金属鉛と金属
銅との反応を抑えている。従って、低融点の鉛が銅中に
固溶することがないため、焼成中に内部電極が端面から
外部に流出するなどの不都合が起こらず、均質な内部電
極を得ることができる。Further, in the present manufacturing method, the reoxidation treatment of the dielectric is performed after the reduction treatment, thereby suppressing the reaction between metallic lead and metallic copper generated by the reduction of the dielectric during the firing of the dielectric ceramic. . Therefore, since low-melting-point lead does not form a solid solution in copper, there is no inconvenience such as the internal electrode flowing out from the end face during firing, and a homogeneous internal electrode can be obtained.
【００１３】以上のことから、誘電体セラミックの薄膜
化が可能となり、大容量でありながら信頼性が高く、か
つ、安価な積層セラミックコンデンサを得ることができ
る。From the above, it is possible to make the dielectric ceramic thinner, and it is possible to obtain a multilayer ceramic capacitor having a large capacity, high reliability, and low cost.
【００１４】[0014]
【実施例】以下、本発明に係る積層セラミックコンデン
サの製造方法の実施例を図面を参照しつつ詳細に説明す
る。図１において、積層セラミックコンデンサは、複数
個の誘電体セラミック２と、この誘電体セラミック２を
介して互いに積層された状態で配置された静電容量を形
成するための複数個の内部電極１と、内部電極１の所定
のものに接続された静電容量取り出しのための一対の外
部電極３とから構成されている。誘電体セラミック２と
しては誘電率が高く低温焼成可能な鉛系誘電体材料が用
いられている。内部電極１としては安価な卑金属であ
り、電気電導度が高く、また高温での耐酸化性の強い酸
化銅が用いられている。外部電極３の材料としては、ニ
ッケルもしくは銅、またはこれらの合金、ガラスフリッ
トを添加した銅、または銅合金、銀、パラジウム、銀−
パラジウム合金等が挙げられるが積層セラミックコンデ
ンサの使用用途等により適宜な材料を用いることができ
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a method for manufacturing a multilayer ceramic capacitor according to the present invention will be described below in detail with reference to the drawings. In FIG. 1, a multilayer ceramic capacitor includes a plurality of dielectric ceramics 2 and a plurality of internal electrodes 1 for forming a capacitance which are arranged in a state of being laminated with each other via the dielectric ceramics 2. , And a pair of external electrodes 3 connected to a predetermined one of the internal electrodes 1 for taking out capacitance. As the dielectric ceramic 2, a lead-based dielectric material having a high dielectric constant and capable of being fired at a low temperature is used. Copper oxide, which is an inexpensive base metal, has high electric conductivity, and has high oxidation resistance at high temperatures, is used as the internal electrode 1. As a material of the external electrode 3, nickel or copper, or an alloy thereof, copper to which glass frit is added, or a copper alloy, silver, palladium, silver
A palladium alloy or the like can be used, but an appropriate material can be used depending on the intended use of the multilayer ceramic capacitor.
【００１５】ここで、各材料の具体例とコンデンサの製
造工程について詳述する。具体的には誘電体粉末とし
て、１０００℃以下で焼成することの可能な、鉛複合ペ
ロブスカイトを主成分とする誘電体セラミック組成物を
準備した。この誘電体セラミック組成物としては、電気
的特性を発現する主成分として、 ｘＰｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ3−ｙＰｂＴｉＯ3−ｚＰｂ（Ｃｕ1/2Ｗ1/2）Ｏ3 −ｕＺｎＯ−ｖＭｎＯ2 ０．９００≦ｘ≦０．９５０ ０．０４０≦ｙ≦０．０８０ ０．０１０≦ｚ≦０．０３０ （ｘ＋ｙ＋ｚ＝１） ０＜ｕ≦０．０６０ ０＜ｖ≦０．０２０ （ｕ，ｖは重量比）なる
組成物に、焼結を促進する副成分として、 ｘＬｉ2Ｏ−ｙＢａＯ−ｚＢ2Ｏ3−ｗＳｉＯ2 で表され、ｘ，ｙ，ｚ，ｗがそれぞれ ７．０≦ｘ≦８．０ ４１．５≦ｙ≦４３．０ ２０．５≦ｚ≦２２．５ ２８．０≦ｗ≦３０．０ （ｘ＋ｙ＋ｚ＋ｗ＝１） なる組成物であるガラスを添加したものを用いた。Here, specific examples of each material and a manufacturing process of the capacitor will be described in detail. Specifically, a dielectric ceramic composition containing a lead composite perovskite as a main component and capable of being fired at 1000 ° C. or lower was prepared as a dielectric powder. As the dielectric ceramic composition, as a main component expressing the electrical characteristics, xPb (Mg 1/3 Nb 2/3) O 3 -yPbTiO 3 -zPb (Cu 1/2 W 1/2) O 3 - uZnO-vMnO 2 0.900 ≦ x ≦ 0.950 0.040 ≦ y ≦ 0.080 0.010 ≦ z ≦ 0.030 (x + y + z = 1) 0 <u ≦ 0.060 0 <v ≦ 0.020 (u, v weight ratio) to become the composition, as a secondary component to facilitate sintering, is represented by xLi 2 O-yBaO-zB 2 O 3 -wSiO 2, x, y, z, w , respectively 7. 0 ≦ x ≦ 8.0 41.5 ≦ y ≦ 43.0 20.5 ≦ z ≦ 22.5 28.0 ≦ w ≦ 30.0 (x + y + z + w = 1) Using.
【００１６】これに有機溶媒を加え、ボールミルで１６
時間粉砕、混合後、ポリビニルブチラール系のバインダ
ー及び可塑剤を加えてさらに１６時間混合して誘電体セ
ラミックのスラリーを得た。このスラリーをドクターブ
レード法により、ポリエチレンテレフタレート等からな
る厚さ５０μｍのキャリヤフィルム上にシート状に成形
して誘電体セラミックのグリーンシートを得た。An organic solvent was added thereto, and the mixture was ball-milled.
After pulverization and mixing for hours, a polyvinyl butyral-based binder and a plasticizer were added, and the mixture was further mixed for 16 hours to obtain a dielectric ceramic slurry. This slurry was formed into a sheet on a carrier film of polyethylene terephthalate or the like having a thickness of 50 μm by a doctor blade method to obtain a dielectric ceramic green sheet.
【００１７】この誘電体グリーンシートを所定の大きさ
に打ち抜き、その上に酸化銅粉末を用いた内部電極ペー
ストを所定の電極パターンに印刷した。内部電極を印刷
した誘電体グリーンシートを所定の枚数積み重ね、ユニ
ットに強度を持たせるために印刷を行っていないダミー
のグリーンシートを適宜積み重ねた後、７０℃で熱圧着
した。得られた圧着体を所定の大きさに切断して、積層
セラミックコンデンサの生ユニットを得た。This dielectric green sheet was punched into a predetermined size, and an internal electrode paste using a copper oxide powder was printed thereon in a predetermined electrode pattern. A predetermined number of dielectric green sheets on which internal electrodes were printed were stacked, and dummy green sheets on which no printing had been performed were appropriately stacked in order to impart strength to the unit. The obtained crimped body was cut into a predetermined size to obtain a green unit of a multilayer ceramic capacitor.
【００１８】得られた生ユニットを空気中で４５０℃、
１０時間保持することで脱バインダーした後、Ｈ2ガス
中で３５０℃、４時間保持して内部電極の還元処理を行
った。還元後のユニットを、Ｎ2，Ｈ2，Ｏ2の混合ガス
を用いて、内部電極が酸化しない還元性雰囲気に調節し
た内径１０ｃｍの管状炉に入れて、１０００℃で２時間
保持して焼成し、積層セラミックコンデンサを得た。The obtained raw unit is heated at 450 ° C. in air.
After the binder was removed by holding for 10 hours, the internal electrode was reduced by holding at 350 ° C. for 4 hours in H 2 gas. The reduced unit is placed in a tubular furnace having an inner diameter of 10 cm adjusted to a reducing atmosphere in which the internal electrode is not oxidized using a mixed gas of N 2 , H 2 , and O 2 , and held at 1000 ° C. for 2 hours for firing. Thus, a multilayer ceramic capacitor was obtained.
【００１９】その際、予め８００℃までの温度域におい
て内部電極の銅が酸化せず、誘電体のみ再酸化されるよ
うなＯ2ガスの導入量を実験的に求めておき、前記焼成
中にも８００℃までの温度域においてＯ2ガスを前記の
量だけ導入し、誘電体の再酸化を行った。本実施例で
は、０〜８００℃の温度範囲において、２００リットル
／時間のＮ 2ガスに加えて、１０ｃｃ／時間のＯ2を導入
した。At this time, the temperature range must be up to 800 ° C.
The internal electrode copper is not oxidized, only the dielectric is re-oxidized.
Una OTwoThe amount of gas introduced is determined experimentally, and
In the temperature range up to 800 ° CTwoGas
The amount was introduced and the dielectric was reoxidized. In this embodiment
Is 200 liters in a temperature range of 0 to 800 ° C.
/ Hour N TwoIn addition to gas, 10cc / hour of OTwoIntroduce
did.
【００２０】得られた積層セラミックコンデンサの試料
について、２５℃、１ｋＨｚ、１Ｖｒｍｓでの比誘電率
（εｒ）と誘電損失（ＤＦ）及び絶縁抵抗（ＩＲ）を測
定した。以上の試験による測定結果は以下の第１表の通
りである。The relative dielectric constant (εr), dielectric loss (DF), and insulation resistance (IR) at 25 ° C., 1 kHz, and 1 Vrms were measured for the obtained multilayer ceramic capacitor sample. The measurement results of the above test are shown in Table 1 below.
【００２１】[0021]
【表１】 [Table 1]
【００２２】また、比較例として、前述の誘電体グリー
ンシート上に金属銅粉末を用いた内部電極ペーストによ
り内部電極パターンを印刷して積層セラミックコンデン
サの生ユニットを作製し、脱バインダーを行い、還元処
理及び再酸化処理を行わずに焼成した後、同様に電気的
特性の測定を行った。その結果を以下の第２表に示す。As a comparative example, an internal electrode pattern was printed on the above-mentioned dielectric green sheet with an internal electrode paste using metallic copper powder to produce a raw unit of a multilayer ceramic capacitor, which was subjected to binder removal and reduction. After firing without performing the treatment and the re-oxidation treatment, the electrical characteristics were measured in the same manner. The results are shown in Table 2 below.
【００２３】[0023]
【表２】 [Table 2]
【００２４】前記第１表、第２表からわかるように、本
実施例の積層セラミックコンデンサは、従来の内部電極
を金属銅ペーストのスクリーン印刷により形成する方法
で製造された積層セラミックコンデンサと比較して、遜
色のない比誘電率及び高い絶縁抵抗を有する。また、金
属銅ペーストのスクリーン印刷により内部電極を形成し
た積層セラミックコンデンサでは、脱バインダー時に銅
の酸化膨張によるデラミネーションやクラックの発生が
起こったが、本実施例の積層セラミックコンデンサで
は、脱バインダー時の銅電極の酸化膨張によるデラミネ
ーションやクラックの発生は見られなかった。As can be seen from Tables 1 and 2, the multilayer ceramic capacitor of the present embodiment is compared with a conventional multilayer ceramic capacitor manufactured by a method of forming internal electrodes by screen printing of a metal copper paste. It has comparable dielectric constant and high insulation resistance. In the case of a multilayer ceramic capacitor in which internal electrodes were formed by screen printing of a metal copper paste, delamination and cracks occurred due to oxidative expansion of copper at the time of binder removal. No delamination or cracking due to oxidation expansion of the copper electrode was observed.
【００２５】さらに、いまひとつの比較例として、誘電
体グリーンシート上に酸化銅粉末を用いた内部電極ペー
ストにより内部電極パターンを印刷して積層セラミック
コンデンサの生ユニットを作製し、実施例と同様の脱バ
インダーと内部電極の還元処理を行い、誘電体の再酸化
処理をせずにそのまま焼成した。この場合、１０００℃
焼成の後も積層セラミックコンデンサとして良好な焼結
体は得られず、誘電体は黒色を呈して還元された状態で
あることを示しており、また還元した鉛と内部電極の銅
が反応したために生じる内部電極の溶解が発生し、電気
的特性を測定することができなかった。Further, as another comparative example, an internal electrode pattern was printed on a dielectric green sheet with an internal electrode paste using copper oxide powder to produce a raw unit of a multilayer ceramic capacitor. The binder and the internal electrode were subjected to a reduction treatment, and were baked as they were without a reoxidation treatment of the dielectric. In this case, 1000 ° C
Even after firing, a good sintered body was not obtained as a multilayer ceramic capacitor, indicating that the dielectric was black and reduced, and that the reduced lead and the copper of the internal electrode reacted with each other. Dissolution of the resulting internal electrode occurred, and electrical characteristics could not be measured.
【００２６】なお、本発明に係る積層セラミックコンデ
ンサの製造方法は、前記実施例に限定されるものではな
く、その要旨の範囲内で種々に変更可能である。例え
ば、内部電極として金属銅ペーストを用い、内部電極ペ
ーストを印刷した誘電体グリーンシートを積み重ねて積
層セラミックコンデンサの生ユニットを準備し、これを
脱バインダーして内部電極の銅を僅かに酸化したものに
ついても、この方法を実施することにより、同様の効果
が得られる。The method of manufacturing the multilayer ceramic capacitor according to the present invention is not limited to the above embodiment, but can be variously modified within the scope of the invention. For example, using a metal copper paste as an internal electrode, stacking dielectric green sheets printed with the internal electrode paste to prepare a raw unit of a multilayer ceramic capacitor, debinding and slightly oxidizing copper of the internal electrode The same effect can be obtained by implementing this method.
【００２７】[0027]
【発明の効果】以上の説明で明らかなように、本発明に
よれば、バインダー成分を除去した後に誘電体と内部電
極を共に還元させ、その後に内部電極が酸化せず、誘電
体が酸化する雰囲気中で熱処理する工程を経て誘電体と
内部電極を焼成するようにしたため、誘電体を薄層化し
てもデラミネーションやクラックの発生がなく、内部電
極の誘電体への拡散を抑えて高抵抗、高容量の信頼性の
高い積層セラミックコンデンサを得ることができる。As is apparent from the above description, according to the present invention, after removing the binder component, both the dielectric and the internal electrode are reduced, and thereafter the internal electrode is not oxidized but the dielectric is oxidized. Since the dielectric and internal electrode are fired through a heat treatment process in an atmosphere, there is no delamination or cracking even if the dielectric is made thin, and the internal electrode is suppressed from diffusing into the dielectric and has a high resistance. Thus, a highly reliable multilayer ceramic capacitor having a high capacitance can be obtained.
【図１】本発明の一実施例によって得られた積層セラミ
ックコンデンサを示す断面図。FIG. 1 is a sectional view showing a multilayer ceramic capacitor obtained according to an embodiment of the present invention.
１…内部電極 ２…誘電体セラミック ３…外部電極 DESCRIPTION OF SYMBOLS 1 ... Internal electrode 2 ... Dielectric ceramic 3 ... External electrode
フロントページの続き 合議体 審判長 下野 和行 審判官 田口 英雄 審判官 今井 義男 (56)参考文献 特開 昭63−15407（ＪＰ，Ａ) 特開 平１−230214（ＪＰ，Ａ)Continued on the front page Judge Kazuyuki Shimono Judge Hideo Taguchi Judge Judge Imai Yoshio (56) References JP-A-63-15407 (JP, A) JP-A-1-230214 (JP, A)
Claims (1)
セラミックコンデンサの製造方法において、 バインダー成分を除去した後に誘電体と内部電極を共に
還元させる工程と、 前記還元工程の後に、内部電極が酸化せず、誘電体が酸
化する雰囲気中で前記誘電体と内部電極を焼成する工程
と、 を備えたことを特徴とする積層セラミックコンデンサの
製造方法。1. A method of manufacturing a multilayer ceramic capacitor using copper or a copper alloy as an internal electrode, wherein a step of reducing both the dielectric and the internal electrode after removing a binder component; And baking the dielectric and the internal electrode in an atmosphere in which the dielectric is oxidized without performing the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03239397A JP3142014B2 (en) | 1991-09-19 | 1991-09-19 | Manufacturing method of multilayer ceramic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03239397A JP3142014B2 (en) | 1991-09-19 | 1991-09-19 | Manufacturing method of multilayer ceramic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0582387A JPH0582387A (en) | 1993-04-02 |
| JP3142014B2 true JP3142014B2 (en) | 2001-03-07 |
Family
ID=17044174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03239397A Expired - Lifetime JP3142014B2 (en) | 1991-09-19 | 1991-09-19 | Manufacturing method of multilayer ceramic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3142014B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970008754B1 (en) * | 1994-12-23 | 1997-05-28 | Korea Inst Sci & Tech | Multilayer ceramic capacitor and production thereof |
| DE10164326A1 (en) | 2000-12-28 | 2002-10-31 | Denso Corp | Integrally fired, layered electromechanical conversion element |
| JP4225033B2 (en) | 2001-12-14 | 2009-02-18 | 株式会社日本自動車部品総合研究所 | Ceramic laminate and manufacturing method thereof |
| JP4631246B2 (en) | 2002-03-20 | 2011-02-16 | 株式会社豊田中央研究所 | Piezoelectric ceramic composition, manufacturing method thereof, piezoelectric element and dielectric element |
| US7150838B2 (en) | 2002-03-20 | 2006-12-19 | Denso Corporation | Piezoelectric ceramic composition, its production method and piezoelectric device |
| JP3884669B2 (en) | 2002-04-05 | 2007-02-21 | 株式会社デンソー | Method for manufacturing ceramic laminate |
| DE10351377A1 (en) | 2002-11-05 | 2004-10-28 | Nippon Soken, Inc., Nishio | Laminated dielectric element and method for its production |
| US7531947B2 (en) | 2004-09-07 | 2009-05-12 | Nippon Soken, Inc. | Stacked piezoelectric element and production method thereof |
| WO2024185365A1 (en) * | 2023-03-09 | 2024-09-12 | 太陽誘電株式会社 | Multilayer ceramic electronic component and production method therefor |
-
1991
- 1991-09-19 JP JP03239397A patent/JP3142014B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0582387A (en) | 1993-04-02 |
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