JPH03241723A - Manufacture of laminated ceramic capacitor - Google Patents
Manufacture of laminated ceramic capacitorInfo
- Publication number
- JPH03241723A JPH03241723A JP30078790A JP30078790A JPH03241723A JP H03241723 A JPH03241723 A JP H03241723A JP 30078790 A JP30078790 A JP 30078790A JP 30078790 A JP30078790 A JP 30078790A JP H03241723 A JPH03241723 A JP H03241723A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- atmosphere
- metal
- sintering
- organic binder
- 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.)
- Pending
Links
- 239000003985 ceramic capacitor Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000003989 dielectric material Substances 0.000 claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子機器に用いられる積層セラミックコンデ
ンサに関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a multilayer ceramic capacitor used in electronic equipment.
従来の技術
積層コンデンサは、電極と誘電体セラミックス材料とが
層状に構成されているもので、セラミックス作製技術に
よって一体化、固体化されるため小型、大容量のものが
得られる。さらに電極が内蔵されるため、磁気誘導成分
が少なく高周波用途にも優れた性能を示す。またチップ
型は、リード線がないので部品実装の際、直付けが可能
で電子機器の小型軽量化への要求にもマツチし、今後谷
径発展が期待されている。Conventional multilayer capacitors are composed of layers of electrodes and dielectric ceramic materials, and are integrated and solidified using ceramic manufacturing technology, making it possible to obtain small capacitors with large capacitance. Furthermore, since the electrode is built-in, there is little magnetic induction component and it exhibits excellent performance in high-frequency applications. In addition, the chip type does not have lead wires, so it can be directly attached when mounting components, and it meets the demand for smaller and lighter electronic devices, so it is expected that the diameter will continue to grow in the future.
一方、コンデンサの材質における分類から、アルミ電解
、タンタル電解１紙、有機フィルムなどが上げられ、積
層セラミックコンデンサの容量範囲から、それらのすべ
てと競合関係にある。したがって、積層セラミックコン
デンサの今後に要求される項目としては、大容量化、小
型化、高信顛性、低価格化などが上げられ、特に低価格
化に対する要求は、大きいものがある。そして価格を決
定する構成要素としては、使用される内部電極に負うと
ころが大であり、積層セラミックコンデンサのコストが
電極材料によって左右されると言っても過言ではない。On the other hand, the classification of capacitor materials includes aluminum electrolytic, tantalum electrolytic 1 paper, organic film, etc., and multilayer ceramic capacitors are in competition with all of them due to their capacity range. Therefore, future requirements for multilayer ceramic capacitors include larger capacity, smaller size, higher reliability, lower price, etc., and there is a particularly strong demand for lower prices. The component that determines the price is largely determined by the internal electrodes used, and it is no exaggeration to say that the cost of a multilayer ceramic capacitor is influenced by the electrode material.
一般に用いられる内部電極用金属として、Ｐｔ、Ｐｄ、
Ａｕ、Ａｇが上げられるが、誘電体と同時焼成する必要
性から、誘電体焼結温度より高い融点を持つものを選ば
ねばならない。Ｐｔ、Ｐｄ、Ａｕ、Ａｇの融点はそれぞ
れ１７７３℃、１５５５°Ｃ，１０６３°Ｃ，９６０，
５°Ｃであり、Ａｕは価格が高いために使用されること
はなく、またＡｇは融点が低いため単体で使用されるこ
とはない。通常はＰｄ単独で使用されるか、もしくはＰ
ｔ−Ｐｄ−Ａｕ、Ｐｔ−Ｐｄの合金として使用され、積
層コンデンサの中で、内部電極のコストの占める割合が
高いのは、以上のような理由による。そしてこれらのコ
ストダウンを目ざして各方面で種々の検討がなされてい
る。中でも、これらの貴金属のうちで比較的コストの安
いＡｇに注目しＡｇをいかに多く使用するか、つまり、
より低温で焼結する誘電体材料を開発するという方法が
ある。この技術を低温焼結材料技術と呼び各方面で検討
がなされている（例えば、特開昭４９−１９３９９号公
報、Ｅ、Ｃ，５ｕｄｂｒａｏ：ＪＰｈｙｓ、Ｃｈｅｍ、
５ｏｌｉｓｌｓ、２３６． ６５ （１９６２） ）。Commonly used metals for internal electrodes include Pt, Pd,
Au and Ag are examples, but since it is necessary to sinter the material simultaneously with the dielectric material, it is necessary to select one having a melting point higher than the dielectric material sintering temperature. The melting points of Pt, Pd, Au, and Ag are 1773°C, 1555°C, 1063°C, 960°C, respectively.
5° C., Au is not used because it is expensive, and Ag is not used alone because its melting point is low. Usually Pd is used alone or Pd
The reason why internal electrodes are used as alloys of t-Pd-Au and Pt-Pd and accounts for a high cost in multilayer capacitors is as described above. Various studies are being conducted in various fields with the aim of reducing these costs. Among these precious metals, we are focusing on Ag, which has a relatively low cost, and how to use as much Ag as possible.
One method is to develop dielectric materials that sinter at lower temperatures. This technology is called low-temperature sintering material technology and has been studied in various fields (for example, Japanese Patent Application Laid-Open No. 1939-1939, E, C, 5udbrao: JPhys, Chem,
5olisls, 236. 65 (1962)).
一方、Ａｇでもコストが高いとし、卑金属化を指向する
方向もある。しかしこの方法は、卑金属電極を内部電極
として使用するので、非酸化性雰囲気で誘電体材料と同
時焼成する必要がある。そのため、誘電体材料も非酸化
性雰囲気で還元されないセラミック材料でなければなら
ない。通常用いられるＢ ａ Ｔ ｉＯＢ系誘電体材料
は、その構成元素が還元されてしまうた′め、誘電性を
示さなくなる。したがって電極材料にとっては還元性で
、誘電体材料にとっては非還元性である酸素分圧で焼成
を行なう必要がある。これらの非還元性セラミック誘電
体材料の開発も一部には行なわれている（例えば、特開
昭６５−６７５６８号公報）。On the other hand, there is a tendency to use Ag as a base metal because the cost is high. However, since this method uses base metal electrodes as internal electrodes, it is necessary to co-fire with the dielectric material in a non-oxidizing atmosphere. Therefore, the dielectric material must also be a ceramic material that is not reduced in a non-oxidizing atmosphere. The commonly used B a TiOB dielectric material no longer exhibits dielectric properties because its constituent elements are reduced. Therefore, it is necessary to perform firing at an oxygen partial pressure that is reducing for the electrode material and non-reducing for the dielectric material. Some of these non-reducible ceramic dielectric materials have also been developed (for example, Japanese Patent Laid-Open No. 65-67568).
発明が解決しようとする課題
しかしながら、上記のような非還元性セラミック誘電体
材料が開発されても、克服すべき問題点が残る。それは
、内部電極と誘電体材料を同時焼成するときに有機バイ
ンダの使用に困難が生ずる点にある。つまり誘電体を焼
成する前の生シートに用いられる有機バインダ、および
電極ペーストに含まれる同じく有機バインダが非酸化性
雰囲気では完全に除去するのが困難で、特に焼成温度が
低い場合はさらに分解、除去が困難である。そして完全
に除去できなければセラミック誘電体材料そのものも多
孔質のままで存在するといわれており、焼結が進行しな
いばかりか、分解後のカーボンのため黒ずんだものしか
得られない。したがって卑金属を内部電極とする積層セ
ラミックコンデンサの実用化は、以上の理由で困難とさ
れている。Problems to be Solved by the Invention However, even if non-reducible ceramic dielectric materials such as those described above are developed, problems remain to be overcome. The problem is that the use of an organic binder poses difficulties when co-firing the internal electrodes and the dielectric material. In other words, the organic binder used in the raw sheet before firing the dielectric and the same organic binder contained in the electrode paste are difficult to completely remove in a non-oxidizing atmosphere, and especially if the firing temperature is low, they may further decompose. Difficult to remove. It is said that if it cannot be completely removed, the ceramic dielectric material itself will remain porous, and not only will sintering not proceed, but only a blackened material will be obtained due to the decomposed carbon. Therefore, it is difficult to put a multilayer ceramic capacitor using a base metal as an internal electrode into practical use for the above reasons.
本発明は上記の問題点に鑑み、積層コンデンサを形成す
る方法として、新しい脱バインダ方法を提供するととも
に、本方法によって始めて得られた構造を有する積層セ
ラミックコンデンサを提供するものである。In view of the above problems, the present invention provides a new binder removal method as a method for forming a multilayer capacitor, and also provides a multilayer ceramic capacitor having a structure obtained for the first time by this method.
課題を解決するための手段
上記の問題点を解決するため本発明の積層コンデンサは
、セラミック誘電体材料に有機バインダ。Means for Solving the Problems In order to solve the above problems, the multilayer capacitor of the present invention uses an organic binder in a ceramic dielectric material.
可望剤を加えてグリーンシートとしたものを用い、この
グリーンシート上に鉄、ニッケル、コバルト。A green sheet is created by adding a desensitizer, and iron, nickel, and cobalt are placed on top of this green sheet.
銅もしくは、それらの混合物を酸化物の形でペースト化
したものでパターニングし、これらを複数枚積層して所
望の寸法に切断する。A paste made of copper or a mixture thereof in the form of an oxide is patterned, and a plurality of these are laminated and cut into desired dimensions.
次に脱バインダの方法は、セラミック誘電体材料の焼結
が進行するより低い温度で、充分にバインダ成分が分解
される空気中のような酸化雰囲気で熱処理を行なう。こ
の時、前記金属酸化物粉は、必要以上の焼結も構造変態
も行なわれずに有機バインダが除去されるものである。Next, the method for removing the binder is to perform heat treatment in an oxidizing atmosphere such as air, where the binder component is sufficiently decomposed at a temperature lower than that at which sintering of the ceramic dielectric material proceeds. At this time, the metal oxide powder is such that the organic binder is removed without excessive sintering or structural transformation.
次に還元雰囲気での熱処理で前記金属酸化物を金属に還
元し、その後窒素雰囲気中で焼成を行ない、誘電体と前
記金属の焼結が進行してコンデンサが形成される。Next, the metal oxide is reduced to metal by heat treatment in a reducing atmosphere, and then firing is performed in a nitrogen atmosphere to progress sintering of the dielectric and the metal to form a capacitor.
作用
本発明は、上記の構成によって非酸化性雰囲気中での脱
バインダが可能になった。つまり出発原料に金属酸化物
を用いることで、脱バインダ時には、有機バインダの分
解、除去のみを、還元時には、金属酸化物の還元のみを
考慮すればよい訳であり、従来のように微妙なコントロ
ールを必要とした作製時の雰囲気も、脱バインダ時は空
気中、還元はＮ２中もしくはＨ２を含むＮ２中で行ない
、焼成は単にＮ２中の雰囲気で行なえばよい。Function: With the above-described structure, the present invention enables binder removal in a non-oxidizing atmosphere. In other words, by using a metal oxide as a starting material, only the decomposition and removal of the organic binder needs to be considered during debinding, and only the reduction of the metal oxide needs to be considered during reduction, which requires less delicate control than in the past. Regarding the atmosphere during production which requires , the binder removal is performed in air, reduction is performed in N 2 or N 2 containing H 2 , and firing is performed simply in an atmosphere of N 2 .
また、前記脱バインダ処理工程では、処理温度をコント
ロールすることで、金属酸化物を誘電体中に所望の深さ
で拡散させることができる。これにより内部電極と、誘
電体材料との接着を向上させる上で著しい効果がある。Furthermore, in the binder removal treatment step, the metal oxide can be diffused into the dielectric to a desired depth by controlling the treatment temperature. This has a significant effect on improving the adhesion between the internal electrodes and the dielectric material.
図にその構成である積層コンデンサの断面図を示す。図
中の内部電極層２と誘電体層１の界面に前述の金属酸化
物拡散層３が存在する。The figure shows a cross-sectional view of a multilayer capacitor with this configuration. The aforementioned metal oxide diffusion layer 3 exists at the interface between the internal electrode layer 2 and the dielectric layer 1 in the figure.
実施例
まず本発明にかかるセラミック誘電体材料は、組成式が
（Ｓ ｒｏ、７ 、 Ｃａｏ、＋ ） −Ｔ ｉ
ｏ８となるように、５ｒＣｏ３．ＣａＣｏ３．ＴｉＯ２
を出発原料として、湿式混合、乾燥したものを１２００
°Ｃ（空気中）で仮焼粉砕したものを用い、さらに低温
焼結化のためガラス成分を添加した。Examples First, a ceramic dielectric material according to the present invention has a compositional formula of (S ro, 7 , Cao, + ) −T i
o8, 5rCo3. CaCo3. TiO2
As a starting material, wet mix and dry 1200
The material was calcined and pulverized at °C (in air), and a glass component was added for low-temperature sintering.
ガラス材料としては、例えば、Ｂａｄ、Ｂ２Ｏ３゜Ｃａ
ｂ、ＭｇＯ，Ａｆ２０８．Ｓ ｉ０２などの成分から構
成されるガラスを用いた。以上のような誘電体材料とガ
ラス材料をそれぞれ重量比で７０対３０となるように混
合する。これらの成分は熱力学的に安定で鉄やニッケル
、コバルト、銅のそれぞれの金属を酸化させることはな
い。次にこれらの成分からなる粉末を有機バインダとし
てのポリビニルブチラール、可塑剤としてのデーｎ−ブ
チルフタレート溶剤としてのトルエンとを混合し、スラ
リーとした。組成比は、上記無機成分を１００として重
量比でポリビニルブチラールを１０部、デーｎ−プチル
フタレー十を５部、トルエンを４０部である。Examples of glass materials include Bad, B2O3°Ca
b, MgO, Af208. A glass composed of components such as Si02 was used. The dielectric material and glass material as described above are mixed in a weight ratio of 70:30. These components are thermodynamically stable and do not oxidize iron, nickel, cobalt, or copper. Next, the powder consisting of these components was mixed with polyvinyl butyral as an organic binder, de-n-butyl phthalate as a plasticizer, and toluene as a solvent to form a slurry. The composition ratio is 10 parts by weight of polyvinyl butyral, 5 parts of D-n-butyl phthalate, and 40 parts of toluene, with the above inorganic component being 100 parts.
このスラリーを、ドクタブレード法で有機フィルム上に
シート成型した。この時のグリーンシートの厚みは乾燥
後で約６０μｍとした。次にこのグリーンシート上に平
気粒径２．５μｍの酸化コバルトＣｏｏ粉末からなるペ
ーストを用いて、所望のパターンになるようスクリーン
印刷を行なった。This slurry was formed into a sheet on an organic film using a doctor blade method. The thickness of the green sheet at this time was approximately 60 μm after drying. Next, screen printing was performed on this green sheet using a paste made of cobalt oxide Coo powder having an average particle size of 2.5 μm so as to form a desired pattern.
ペースト作製のための条件は、溶剤としてのテレピン油
に、有機バインダのエチルセルロースを溶かしたものを
用い、上記酸化コバルト粉末と３段ロールにて混練した
ものを用いた。以上のようにして得られた電極パターン
形成済グリーンシートを、内部電極パターンが対向する
ように２０枚重ね合わせ、熱圧着して一体化した。さら
に所定の寸法に打ち抜いたものを、まず、脱バインダを
行なう。この脱バインダ後程は、空気中で、７００°Ｃ
の温度まで加熱して、前記グリーンシート内および酸化
コバルトペースト内に含まれる有機バインダ成分の分解
および除去を行なうものである。The conditions for preparing the paste were as follows: ethyl cellulose as an organic binder was dissolved in turpentine oil as a solvent, and the mixture was kneaded with the above-mentioned cobalt oxide powder using a three-stage roll. Twenty of the electrode pattern-formed green sheets obtained as described above were stacked one on top of the other so that the internal electrode patterns faced each other, and were bonded together by thermocompression. Furthermore, the binder is removed from the punched piece having a predetermined size. After this binder removal step, the temperature is 700°C in air.
The organic binder component contained in the green sheet and the cobalt oxide paste is decomposed and removed by heating to a temperature of .
この脱バインダ後の素体を走査型電子顕微鏡で観察した
ところ、セラミック誘電体材料の焼結の進行が見られず
、またガラス成分の溶媒、軟化も認められなかった。さ
らに組成分析でも、素体中にカーンンの存在は見られず
、有機成分が完全に除去できたことが確認された。次に
この脱バインダ済みの素体を還元する。還元条件は水素
２０％を含む窒素雰囲気中で４００ ”Ｃの温度で２時
間処理して行なった。このときの素子をＸ線回折で分析
の結果、誘電体、およびガラス成分は温度が低いのでな
んの変化もなく電極材料の酸化コバルトのみが金属コバ
ルトに変化した。次の焼成を行なう。When the element body after the binder was removed was observed with a scanning electron microscope, no progress of sintering of the ceramic dielectric material was observed, and no solvent or softening of the glass component was observed. Furthermore, compositional analysis revealed no presence of carnine in the element, confirming that organic components were completely removed. Next, this binder-removed element body is reduced. The reduction conditions were a 2 hour treatment at 400''C in a nitrogen atmosphere containing 20% hydrogen.An analysis of the element at this time by X-ray diffraction revealed that the dielectric and glass components were at a low temperature. Only the cobalt oxide of the electrode material changed to metallic cobalt without any change.The next firing was performed.
焼成は、純窒素雰囲気中で１２００″Ｃの温度で２時間
保持して行なった。昇降温スピードは３００’Ｃ／ ｈ
ｒで行なった。本工程により誘電体の焼結が進行しち
密化が行なわれた。そして、内部電極材料のコバルト粉
の焼結も起こり、一体化される。Firing was carried out in a pure nitrogen atmosphere by holding the temperature at 1200'C for 2 hours.The heating and cooling speed was 300'C/h.
I did it with r. Through this step, the dielectric material was sintered and densified. Then, sintering of the cobalt powder, which is the material for the internal electrodes, takes place and is integrated.
以上のようにして得られた積層コンデンサ焼結体を、外
部電極としてｌＮ−Ｇａを塗布し特性を測定した。その
結果は以下の通りであり、充分実用に供するものである
。The multilayer capacitor sintered body obtained as described above was coated with lN-Ga as an external electrode, and its characteristics were measured. The results are as follows, and are sufficiently useful for practical use.
電極面積 ４胴Ｘ ３ ｍｍ
厚さ １．０ｍｍ
容量 ０．０８μＦ
ｔａｎ６ ５．０％
絶縁抵抗 ５．２Ｘ１０８Ω
実施例２
セラミック誘電体材料に（（Ｂ ａ ｏ、 ｂｑ・Ｃａ
、、。２・Ｓｒ、。３）Ｏ）１．ＯＩＴ ｉ０２なる
組成比となるようにＢａｃｏ８．ＣａＣＯ３，５ｒＣｏ
３゜Ｔ ｉ Ｏ２を混合仮焼したものを用いた。本材料
は実施例１と同じく、鉄、ニッケル、コバルト、銅を酸
化させることはない。そして、電極材料には、平均粒径
２μｍの酸化ニッケル粉と平均粒径１．０μｍの酸化第
二銅を、重量比で５０対５０になるよう混合したものを
用いた。次に実施例１と同様の方法で積層したグリーン
シートを作製し、所定の寸法に打ち抜いた。さらに同様
の方法で、脱バインダ、還元、焼成を行なった。Electrode area 4 bodies
,,. 2.Sr. 3)O)1. Baco8. CaCO3,5rCo
A mixed and calcined mixture of 3°T i O2 was used. Similar to Example 1, this material does not oxidize iron, nickel, cobalt, and copper. As the electrode material, a mixture of nickel oxide powder having an average particle size of 2 μm and cupric oxide having an average particle size of 1.0 μm was used in a weight ratio of 50:50. Next, a laminated green sheet was produced in the same manner as in Example 1, and punched into a predetermined size. Further, binder removal, reduction, and firing were performed in the same manner.
還元は３００ ”Ｃで２時間水素１００％の雰囲気で行
なった。また焼成は、純窒素雰囲気で１
１２５０°Ｃの温度で行なった。得られた焼結体に外部
電極（Ｉｎ−Ｇａ）を塗布し特性を測定した結果は以下
の通りである。Reduction was carried out at 300"C for 2 hours in an atmosphere of 100% hydrogen. Calcination was carried out at a temperature of 11250°C in a pure nitrogen atmosphere. An external electrode (In-Ga) was attached to the obtained sintered body. The results of coating and measuring the characteristics are as follows.
静電容量 ０．７４μＦ
ｊａｎ６ ２．０％
絶縁抵抗 ７．８Ｘ１０９Ω
以上の実施例において、誘電体材料に（Ｓｒ・Ｃａ）Ｔ
ｉｅ、系および（（Ｂａ−Ｃａ−３ｒ）０）ＴＩ０２系
材料を用いたが、還元雰囲気焼成で還元されず、比抵抗
を下げない誘電体材料であれば、どのような材料でも良
いのはいうまでもない。また電極材料に、酸化コバルト
粉および酸化ニッケル、酸化第二銅混合粉を用いたが、
この他、酸化鉄粉やそれぞれの混合粉を用いてもよい。Capacitance 0.74μF jan6 2.0% Insulation resistance 7.8X109Ω In the above examples, (Sr・Ca)T is used as the dielectric material
ie, and ((Ba-Ca-3r)0)TI02-based materials were used, but any dielectric material may be used as long as it is not reduced by firing in a reducing atmosphere and does not lower the resistivity. Needless to say. In addition, cobalt oxide powder, nickel oxide, and cupric oxide mixed powder were used as electrode materials, but
In addition, iron oxide powder or a mixed powder of each may be used.
特に上記実施例において酸化ニッケル、酸化銅粉を用い
たのは、Ｎｉ−Ｃｕが全率固溶であり、使用する誘電体
材料の焼結可能な温度に応じて、その混合割合を変える
ことができるからである。したがって銅の融点である１
０８３°Ｃ以下の温度で焼結し、かつ還元性雰囲気で焼
成可能な誘電体が開２
発できれば、銅のみで内部電極が形成できることは明白
である。In particular, the reason why nickel oxide and copper oxide powders were used in the above examples is that Ni-Cu is completely dissolved in solid solution, and the mixing ratio can be changed depending on the sintering temperature of the dielectric material used. Because you can. Therefore, the melting point of copper is 1
It is clear that if a dielectric material that can be sintered at temperatures below 0.83°C and can be fired in a reducing atmosphere can be developed, internal electrodes can be formed using only copper.
また、本実施例ではグリーンシート積層法により積層体
を形成したが、厚膜印刷法等の他の方法において積層し
たものであっても有効であることはいうまでもない。Further, in this example, the laminate was formed by a green sheet lamination method, but it goes without saying that lamination by other methods such as a thick film printing method is also effective.
発明の効果
以上のように本発明は、積層型セラミックコンデンサの
内部電極の卑金属化のために、極めて有効な手段を提供
するものである。また本方法によって得られる積層型セ
ラミックコンデンサは信鯨性の高い構造を有するもので
ある。Effects of the Invention As described above, the present invention provides extremely effective means for forming base metals in the internal electrodes of multilayer ceramic capacitors. Furthermore, the multilayer ceramic capacitor obtained by this method has a highly reliable structure.
すなわち、脱バインダを空気中で行なうため、特別な有
機バインダを必要とせず、完全なバインダ除去が行なえ
る。また脱バインダの温度条件に応じて、所定の厚みの
金属酸化物の拡散層を形成することができるため、強固
なメタライズが得られる。そして還元時には、金属酸化
物の還元のみを考慮すればよいので、その雰囲気コント
ロールが容易となる。That is, since the binder is removed in air, a special organic binder is not required and the binder can be completely removed. Moreover, since a metal oxide diffusion layer of a predetermined thickness can be formed depending on the temperature conditions of binder removal, strong metallization can be obtained. At the time of reduction, only the reduction of metal oxides needs to be considered, so that the atmosphere can be easily controlled.
さらに焼成時には電極の酸化を防止させるに十分な窒素
雰囲気で焼成が可能となり、同様に焼成時の雰囲気コン
トロールも容易である。Furthermore, during firing, it is possible to perform firing in a nitrogen atmosphere sufficient to prevent oxidation of the electrode, and the atmosphere during firing can also be easily controlled.
本発明は、積層セラミックコンデンサの内部電極を卑金
属化する上で極めて効果的な発明である。The present invention is extremely effective in making the internal electrodes of multilayer ceramic capacitors base metal.
図は本発明の積層セラミックコンデンサの断面図で示し
たものである。
■・・・・・・誘電体材料、２・・・・・・内部電極、
３・・・・・・金属酸化物拡散層、４・・・・・・外部
電極。The figure shows a cross-sectional view of a multilayer ceramic capacitor according to the present invention. ■・・・Dielectric material, 2・・・Internal electrode,
3...Metal oxide diffusion layer, 4...External electrode.
Claims (1)
の合金の融点より低い温度で焼結するセラミック誘電体
材料粉と少なくとも有機バインダ，可塑剤とからなるグ
リーンシート上に、酸化鉄，酸化ニッケル，酸化コバル
ト，酸化銅のいずれかもしくは、それらの混合粉を有機
バインダと有機溶剤とからなるビークルとともに混練し
たペーストを印刷し、パターン膜を形成する工程と、該
印刷されたグリーンシートの複数枚を加熱加圧すること
によって積層する工程と、これを前記セラミック誘電体
材料が焼結し始めない温度の空気中で加熱し、有機バイ
ンダを焼結させる工程と、これを還元雰囲気中で熱処理
し、酸化鉄，酸化ニッケル，酸化コバルト，酸化銅のい
ずれかもしくは、それらの混合粉を金属に還元せしむる
工程と、これを鉄，ニッケル，コバルト，銅のいずれか
または、これらの合金の融点より低い温度の窒素雰囲気
中で焼結し、セラミック誘電体と前記金属とをち密化す
る工程からなる積層セラミックコンデンサの製造方法。Iron oxide, nickel oxide, A process of printing a paste made by kneading cobalt oxide, copper oxide, or a mixed powder thereof with a vehicle consisting of an organic binder and an organic solvent to form a pattern film, and printing a plurality of the printed green sheets. A step of laminating layers by applying heat and pressure, a step of heating this in air at a temperature at which the ceramic dielectric material does not begin to sinter to sinter the organic binder, and a step of heat-treating this in a reducing atmosphere to oxidize it. A process of reducing iron, nickel oxide, cobalt oxide, copper oxide, or a mixed powder thereof to a metal, and reducing the melting point of iron, nickel, cobalt, copper, or an alloy thereof to a metal. A method for manufacturing a multilayer ceramic capacitor comprising the steps of sintering in a nitrogen atmosphere at a high temperature to densify a ceramic dielectric and the metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30078790A JPH03241723A (en) | 1984-12-19 | 1990-11-05 | Manufacture of laminated ceramic capacitor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26901184A JPS61144813A (en) | 1984-12-19 | 1984-12-19 | Laminated ceramic capacitor and manufacture thereof |
| JP30078790A JPH03241723A (en) | 1984-12-19 | 1990-11-05 | Manufacture of laminated ceramic capacitor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26901184A Division JPS61144813A (en) | 1984-12-19 | 1984-12-19 | Laminated ceramic capacitor and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03241723A true JPH03241723A (en) | 1991-10-28 |
Family
ID=26548579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30078790A Pending JPH03241723A (en) | 1984-12-19 | 1990-11-05 | Manufacture of laminated ceramic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03241723A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5041049A (en) * | 1973-05-13 | 1975-04-15 | ||
| JPS54118566A (en) * | 1978-03-06 | 1979-09-14 | Nippon Electric Co | Method of producing laminated ceramic capacitor |
-
1990
- 1990-11-05 JP JP30078790A patent/JPH03241723A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5041049A (en) * | 1973-05-13 | 1975-04-15 | ||
| JPS54118566A (en) * | 1978-03-06 | 1979-09-14 | Nippon Electric Co | Method of producing laminated ceramic capacitor |
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