JP5621671B2 - Manufacturing method of electronic parts - Google Patents

Manufacturing method of electronic parts Download PDF

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JP5621671B2
JP5621671B2 JP2011059109A JP2011059109A JP5621671B2 JP 5621671 B2 JP5621671 B2 JP 5621671B2 JP 2011059109 A JP2011059109 A JP 2011059109A JP 2011059109 A JP2011059109 A JP 2011059109A JP 5621671 B2 JP5621671 B2 JP 5621671B2
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plating film
external electrode
etching
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光典 井上
光典 井上
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Murata Manufacturing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

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  • Ceramic Capacitors (AREA)
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  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Description

本発明は、電子部品の製造方法に関し、詳しくは、外部電極本体の表面に、Ｎｉめっき皮膜およびＡｕめっき皮膜を備えた外部電極を備えた電子部品の製造方法に関する。   The present invention relates to a method for manufacturing an electronic component, and more particularly to a method for manufacturing an electronic component including an external electrode provided with a Ni plating film and an Au plating film on the surface of an external electrode body.

例えば、セラミック多層基板などの電子部品は、通常、その表面に外部電極を備えた構造を有している。   For example, an electronic component such as a ceramic multilayer substrate usually has a structure having external electrodes on its surface.

この外部電極を構成する電極材料の１つに、Ａｇが広く用いられている。しかしながら、Ａｇ電極は、電子部品を構成するセラミックなどの絶縁材料からなる基材の表面をＡｇが移動するマイグレーション現象により、電極間の絶縁抵抗を低下させるという問題点がある。   Ag is widely used as one of electrode materials constituting the external electrode. However, the Ag electrode has a problem in that the insulation resistance between the electrodes is lowered due to a migration phenomenon in which Ag moves on the surface of a base material made of an insulating material such as ceramic constituting an electronic component.

そこで、Ａｇのマイグレーションを防ぐため、Ａｇ電極（外部電極本体）にめっきを施して、その表面にＮｉめっき皮膜やＡｕめっき皮膜などのめっき被膜を形成することが行われている。   Therefore, in order to prevent Ag migration, the Ag electrode (external electrode main body) is plated to form a plating film such as a Ni plating film or an Au plating film on the surface thereof.

しかしながら、Ａｇ電極（外部電極本体）上にめっき皮膜を形成するようにした場合にも、めっき皮膜の形成が不十分で、例えば、図４に示すように、Ａｇ電極（外部電極本体）５１がめっき皮膜５２により完全には被覆されずに、Ａｇ電極（外部電極本体）５１の先端部（周縁部）が、外部に露出しているような場合、Ａｇのマイグレーションにより、電極間の絶縁抵抗の劣化を招くという問題点がある。   However, even when the plating film is formed on the Ag electrode (external electrode body), the formation of the plating film is insufficient. For example, as shown in FIG. When the tip portion (peripheral portion) of the Ag electrode (external electrode main body) 51 is exposed to the outside without being completely covered with the plating film 52, the insulation resistance between the electrodes is reduced due to the migration of Ag. There is a problem of causing deterioration.

そこで、Ａｇ電極（外部電極本体）の周囲の不要部分（滲み出し部分など）を予めエッチングして除去した後、ＮｉめっきとＡｕめっきを施して、Ｎｉめっき皮膜およびＡｕめっき皮膜を形成することが考えられるが、この方法の場合、Ａｇ電極（外部電極本体）の周囲の不要部分をエッチング除去することはできても、その後のめっき工程で、Ａｇ電極（外部電極本体）の先端部（周縁部）が、十分にめっき皮膜により被覆されず、Ａｇのマイグレーションにより電極間の絶縁抵抗の劣化を招くおそれが残るという問題点がある。   Therefore, unnecessary portions (such as exuded portions) around the Ag electrode (external electrode main body) are removed by etching in advance, and then Ni plating and Au plating are performed to form a Ni plating film and an Au plating film. In this method, although the unnecessary portion around the Ag electrode (external electrode main body) can be removed by etching, the tip portion (periphery portion) of the Ag electrode (external electrode main body) is formed in the subsequent plating step. However, it is not sufficiently covered with the plating film, and there is a problem that the migration of Ag may cause deterioration of the insulation resistance between the electrodes.

一方、Ａｇ電極（外部電極本体）に例えばＮｉめっきおよびＡｕめっきを先に施し、その後に、めっき皮膜から露出したＡｇ電極（外部電極本体）の先端部（周縁部）をエッチング除去することも考えられる。しかしながら、この方法の場合、めっき皮膜を形成した後、めっき皮膜の先端部などに露出したＡｇ電極（外部電極本体）を確実にエッチングすることは容易ではなく、不要なＡｇ電極がエッチングされずに残留してマイグレーションを生じるという問題点がある。また、不要なＡｇ電極を十分にエッチング除去できるように強いエッチング液を用いると、Ｎｉめっき皮膜やＡｕめっき皮膜などのめっき皮膜（特にＮｉめっき皮膜）をエッチングしてしまうという問題点がある。   On the other hand, it is also conceivable that the Ag electrode (external electrode body) is first subjected to, for example, Ni plating and Au plating, and then the tip (peripheral part) of the Ag electrode (external electrode body) exposed from the plating film is etched away. It is done. However, in this method, after forming the plating film, it is not easy to reliably etch the Ag electrode (external electrode body) exposed at the tip of the plating film, and unnecessary Ag electrodes are not etched. There is a problem that migration occurs due to the residual. Further, when a strong etching solution is used so that unnecessary Ag electrodes can be sufficiently removed by etching, there is a problem that a plating film (particularly a Ni plating film) such as a Ni plating film or an Au plating film is etched.

特開平１０−６０６７１号公報Japanese Patent Laid-Open No. 10-60671

本発明は、上記課題を解決するものであり、電子部品素体の表面に配設されるＡｇを主成分とする外部電極本体と、その表面を被覆するＮｉめっき皮膜および該Ｎｉめっき皮膜上に形成されるＡｕめっき皮膜とを備えた外部電極を有する電子部品を製造するにあたって、Ａｇのマイグレーションによる絶縁抵抗の劣化を抑制することが可能で、信頼性の高い電子部品を効率よく製造することができる電子部品の製造方法を提供することを目的とする。   SUMMARY OF THE INVENTION The present invention solves the above-described problem, and has an external electrode body mainly composed of Ag disposed on the surface of an electronic component body, a Ni plating film covering the surface, and the Ni plating film. When manufacturing an electronic component having an external electrode provided with an Au plating film to be formed, it is possible to suppress deterioration of insulation resistance due to Ag migration and efficiently manufacture a highly reliable electronic component. An object of the present invention is to provide a method for manufacturing an electronic component.

上記課題を解決するため、本願第１の発明である電子部品の製造方法は、
電子部品素体と、その表面に形成された外部電極とを備えた電子部品の製造方法であって、
Ａｇを主成分とする材料からなる外部電極本体を形成する電極形成工程と、
前記外部電極本体の表面にＮｉめっき皮膜を形成し、その後に、前記Ｎｉめっき皮膜の表面にＡｕめっき皮膜を形成するめっき皮膜形成工程と、
前記めっき皮膜形成工程の後に、鉄（III）塩、過酸化水素、およびペルオキソ２硫酸アンモニウムからなる群より選ばれる少なくとも１種を含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、前記めっき皮膜から露出した前記外部電極本体の端部を除去するエッチング工程と
を備えていることを特徴としている。 In order to solve the above-described problem, a method for manufacturing an electronic component according to the first invention of the present application is as follows:
An electronic component manufacturing method comprising an electronic component element body and an external electrode formed on a surface thereof ,
An electrode forming step of forming an external electrode body made of a material containing Ag as a main component;
Forming a Ni plating film on the surface of the external electrode body, and then forming a Au plating film on the surface of the Ni plating film; and
After the plating film forming step, etching is performed using an etching solution that contains at least one selected from the group consisting of iron (III) salt, hydrogen peroxide, and ammonium peroxodisulfate, and selectively dissolves Ag . And an etching step of removing an end portion of the external electrode body exposed from the plating film .

また、上記課題を解決するため、本願第２の発明である電子部品の製造方法は、電子部品素体と、その表面に形成された外部電極とを備えた電子部品の製造方法であって、
Ａｇを主成分とする材料からなる外部電極本体を形成する電極形成工程と、
前記外部電極本体の表面にＮｉめっき皮膜を形成し、その後に、前記Ｎｉめっき皮膜の表面にＡｕめっき皮膜を形成するめっき皮膜形成工程と、
前記めっき皮膜形成工程の後に、硫酸鉄（III）アンモニウムを含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、前記めっき皮膜から露出した前記外部電極本体の端部を除去するエッチング工程と
を備えていることを特徴としている。 Moreover, in order to solve the above-mentioned problem, a method for manufacturing an electronic component according to the second invention of the present application is a method for manufacturing an electronic component including an electronic component element body and an external electrode formed on the surface thereof.
An electrode forming step of forming an external electrode body made of a material containing Ag as a main component;
Forming a Ni plating film on the surface of the external electrode body, and then forming a Au plating film on the surface of the Ni plating film; and
After the plating film forming step, etching is performed using an etching solution containing iron (III) ammonium sulfate and selectively dissolving Ag to remove the end portion of the external electrode body exposed from the plating film. Process and
It is characterized by having .

また、前記エッチング液として、ｐＨが１．０以上のものを用いることが好ましい。   Further, it is preferable to use an etchant having a pH of 1.0 or more.

第１の発明にかかる電子部品の製造方法は、Ａｇを主成分とする材料からなる外部電極本体（以下単に「Ａｇ電極」ともいう）の表面に、Ｎｉめっき皮膜とＡｕめっき皮膜とを形成した後、鉄（III）塩、過酸化水素、およびペルオキソ２硫酸アンモニウムからなる群より選ばれる少なくとも１種を含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、めっき皮膜から露出した外部電極本体の端部を除去するようにしているので、Ｎｉめっき皮膜およびＡｕめっき皮膜（以下単に「めっき皮膜」ともいう）を溶解させることなく、めっき皮膜から露出した外部電極本体を構成するＡｇのみを効率よくエッチング除去して、Ａｇマイグレーションの発生を抑制することができる。 In the method of manufacturing an electronic component according to the first invention , a Ni plating film and an Au plating film are formed on the surface of an external electrode body (hereinafter also simply referred to as “Ag electrode”) made of a material mainly composed of Ag. Then, an external portion exposed from the plating film is etched using an etching solution containing at least one selected from the group consisting of iron (III) salt, hydrogen peroxide, and ammonium peroxodisulfate and selectively dissolving Ag. Since the end of the electrode body is removed, only the Ag constituting the external electrode body exposed from the plating film without dissolving the Ni plating film and the Au plating film (hereinafter also simply referred to as “plating film”). Can be efficiently removed by etching, and the occurrence of Ag migration can be suppressed.

また、外部電極本体（Ａｇ電極）の、上記めっき皮膜から露出した部分を除去することにより、外部電極間の距離を確保することが可能になり、Ａｇ電極への電界集中を抑制して、マイグレーションの発生を抑えることが可能になる。
その結果、外部電極間の絶縁抵抗の劣化を抑制することが可能で、信頼性の高い電子部品を効率よく製造することが可能になる。 In addition, by removing the portion of the external electrode body (Ag electrode) exposed from the plating film, it becomes possible to secure the distance between the external electrodes, suppress the electric field concentration on the Ag electrode, and migrate Can be suppressed.
As a result, it is possible to suppress deterioration of insulation resistance between the external electrodes, and it is possible to efficiently manufacture highly reliable electronic components.

第２の発明にかかる電子部品の製造方法は、Ａｇを主成分とする材料からなる外部電極本体の表面に、Ｎｉめっき皮膜とＡｕめっき皮膜とを形成した後、硫酸鉄（III）アンモニウムを含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、めっき皮膜から露出した外部電極本体の端部を除去するようにしているので、Ｎｉめっき皮膜およびＡｕめっき皮膜を溶解させることなく、めっき皮膜から露出した外部電極本体を構成するＡｇのみを効率よくエッチング除去して、Ａｇマイグレーションの発生を抑制することができる。According to a second aspect of the present invention, there is provided a method of manufacturing an electronic component, comprising: forming an Ni plating film and an Au plating film on a surface of an external electrode body made of a material containing Ag as a main component; Since etching is performed using an etching solution that selectively dissolves Ag, and the end of the external electrode body exposed from the plating film is removed, the Ni plating film and the Au plating film are not dissolved. Only Ag constituting the external electrode body exposed from the plating film can be efficiently removed by etching to suppress the occurrence of Ag migration.

また、外部電極本体（Ａｇ電極）の、上記めっき皮膜から露出した部分を除去することにより、外部電極間の距離を確保することが可能になり、Ａｇ電極への電界集中を抑制して、マイグレーションの発生を抑えることが可能になる。In addition, by removing the portion of the external electrode body (Ag electrode) exposed from the plating film, it becomes possible to secure the distance between the external electrodes, suppress the electric field concentration on the Ag electrode, and migrate Can be suppressed.
その結果、外部電極間の絶縁抵抗の劣化を抑制することが可能で、信頼性の高い電子部品を効率よく製造することが可能になる。  As a result, it is possible to suppress deterioration of insulation resistance between the external electrodes, and it is possible to efficiently manufacture highly reliable electronic components.

また、エッチング液として、ｐＨが１．０以上のものを用いることにより、さらに確実に、めっき皮膜を溶解させることなく、Ａｇ電極を選択的にエッチングして、信頼性の高い外部電極を備えた電子部品を提供することができる。   Further, by using an etchant having a pH of 1.0 or more, the Ag electrode was selectively etched without further dissolving the plating film, and a highly reliable external electrode was provided. Electronic components can be provided.

(ａ)本発明の電子部品の製造方法により製造される電子部品（セラミック多層基板）を示す断面図、(ｂ)は要部を拡大して示す断面図である。(a) Sectional drawing which shows the electronic component (ceramic multilayer substrate) manufactured by the manufacturing method of the electronic component of this invention, (b) is sectional drawing which expands and shows the principal part. 本発明の電子部品の製造方法および比較例の方法により製造した電子部品（セラミック多層基板）の、絶縁抵抗が劣化するまでの時間を示す図である。It is a figure which shows time until insulation resistance deteriorates of the electronic component (ceramic multilayer substrate) manufactured by the manufacturing method of the electronic component of this invention, and the method of a comparative example. 外部電極本体（Ａｇ電極）にめっきを施してめっき被膜を形成した状態（Ａｇ電極のエッチングを行っていない状態）の外部電極を示す図である。It is a figure which shows the external electrode of the state which plated the external electrode main body (Ag electrode), and formed the plating film (The state which is not etching the Ag electrode). 従来の電子部品の製造方法の問題点を説明する図である。It is a figure explaining the problem of the manufacturing method of the conventional electronic component.

以下に本発明の実施の形態を示して、本発明の特徴とするところをさらに詳しく説明する。   Embodiments of the present invention will be described below to describe the features of the present invention in more detail.

この実施例１では、図１(ａ)，(ｂ)に示すような、電子部品（セラミック多層基板）２０を製造する場合を例にとって説明する。このセラミック多層基板２０は、低温焼結セラミックを用いたセラミック多層基板であって、複数のセラミック層５が積層されてなるセラミック多層基板本体１０と、セラミック多層基板本体（セラミック素体）１０の内部に配設された配線１ａやビアホール導体１ｂなどの内部導体１と、セラミック基板本体１０の表面（上下両主面）に配設された外部電極２とを備えている。   In the first embodiment, a case where an electronic component (ceramic multilayer substrate) 20 as shown in FIGS. 1A and 1B is manufactured will be described as an example. The ceramic multilayer substrate 20 is a ceramic multilayer substrate using a low-temperature sintered ceramic, and includes a ceramic multilayer substrate body 10 in which a plurality of ceramic layers 5 are laminated, and an interior of the ceramic multilayer substrate body (ceramic body) 10. Are provided with internal conductors 1 such as wiring 1a and via-hole conductors 1b, and external electrodes 2 provided on the surface (upper and lower main surfaces) of the ceramic substrate body 10.

そして、この実施例１にかかるセラミック多層基板２０においては、外部電極２は、Ａｇペーストを塗布して焼き付けることにより形成された厚膜電極からなる外部電極本体２ａと、その表面に形成されたＮｉめっき皮膜２ｂと、Ｎｉめっき皮膜の表面を覆うように形成されたＡｕめっき皮膜２ｃとを備えている。   In the ceramic multilayer substrate 20 according to the first embodiment, the external electrode 2 includes an external electrode body 2a made of a thick film electrode formed by applying and baking Ag paste, and Ni formed on the surface thereof. A plating film 2b and an Au plating film 2c formed so as to cover the surface of the Ni plating film are provided.

この実施例１では、上述のセラミック多層基板２０を製造するにあたって、ビアホール用貫通孔に電極ペーストが充填され、かつ、所定の内部電極パターンが形成されたセラミックグリーンシートを積層、圧着し、個々の電子部品素子に切断した後、焼成する工程を経て、セラミック多層基板本体（セラミック素体）１０を形成する。   In this Example 1, when manufacturing the ceramic multilayer substrate 20 described above, ceramic green sheets in which a through hole for a via hole is filled with an electrode paste and a predetermined internal electrode pattern is formed are laminated and pressure-bonded. After cutting into electronic component elements, a ceramic multilayer substrate body (ceramic body) 10 is formed through a firing step.

それから、セラミック多層基板本体（セラミック素体）１０の表面の、外部電極を形成すべき所定の位置にＡｇペーストを塗布して焼き付けることにより、例えば、厚みが約１０μｍの外部電極本体（Ａｇ電極）２ａを形成する。   Then, an Ag paste is applied and baked at a predetermined position on the surface of the ceramic multilayer substrate body (ceramic body) 10 where the external electrodes are to be formed, for example, an external electrode body (Ag electrode) having a thickness of about 10 μm. 2a is formed.

次に、Ｎｉめっきを行って、外部電極本体（Ａｇ電極）２ａの表面に、厚みが約1μｍのＮｉめっき皮膜２ｂを形成し、さらにＡｕめっきを行って、Ｎｉめっき皮膜２ｂ上に、厚みが約０．０５μｍのＡｕめっき皮膜２ｃを形成する。   Next, Ni plating is performed to form a Ni plating film 2b having a thickness of about 1 μm on the surface of the external electrode body (Ag electrode) 2a. Further, Au plating is performed to form a thickness on the Ni plating film 2b. An Au plating film 2c of about 0.05 μm is formed.

それから、外部電極本体（Ａｇ電極）２ａが形成され、その表面にＮｉめっき皮膜２ｂおよびＡｕめっき皮膜２ｃが形成された、めっき済みのセラミック基板本体（セラミック素体）１０に対して、表１に示すようなＡｇを選択的に溶解するエッチング液を用いて、表１の条件１および条件２の条件でエッチングを行った。   Then, the external electrode body (Ag electrode) 2a is formed, and the plated ceramic substrate body (ceramic body) 10 having the Ni plating film 2b and the Au plating film 2c formed on its surface is shown in Table 1. Etching was performed under conditions 1 and 2 in Table 1 using an etching solution that selectively dissolves Ag as shown.

なお、条件１では、硫酸鉄（III）アンモニウムを表１に示すように５０ｇ／ｌとなるように水に溶解したエッチング液を用い、条件２では、硝酸鉄（III）を表１に示すように１０ｇ／ｌとなるように水に溶解したエッチング液を用いてエッチングを行った。   In condition 1, an etching solution in which iron (III) ammonium sulfate is dissolved in water to 50 g / l as shown in Table 1 is used, and in condition 2, iron (III) nitrate is shown in Table 1. Etching was performed using an etching solution dissolved in water so as to be 10 g / l.

Figure 0005621671
Figure 0005621671

そして、エッチングの終了後に、各試料を水洗、乾燥して、図１(ａ)，(ｂ)に示すような、外部電極本体（Ａｇ電極）２ａの表面にＮｉめっき皮膜２ｂおよびＡｕめっき皮膜２ｃが形成された構造を有する外部電極２を備えた電子部品（セラミック多層基板）２０を得た。   Then, after the etching is completed, each sample is washed with water and dried, and the Ni plating film 2b and the Au plating film 2c are formed on the surface of the external electrode body (Ag electrode) 2a as shown in FIGS. 1 (a) and 1 (b). As a result, an electronic component (ceramic multilayer substrate) 20 including the external electrode 2 having a structure in which is formed was obtained.

それから、エッチング後の各試料について、表２に示すような条件で、水中電圧印加試験を実施して、絶縁抵抗が劣化するまでの時間を調べ、マイグレーション特性を評価した。   Then, an underwater voltage application test was performed on each sample after etching under the conditions shown in Table 2, the time until the insulation resistance deteriorated was examined, and the migration characteristics were evaluated.

また、比較のため、エッチングを行わない試料を作製して、同様の方法で、絶縁抵抗が劣化するまでの時間を調べ、マイグレーション特性を評価した。
その結果を図２に示す。 For comparison, a sample that was not etched was prepared, and the time until the insulation resistance deteriorated was examined by the same method to evaluate the migration characteristics.
The result is shown in FIG.

Figure 0005621671
Figure 0005621671

図２に示すように、水中電圧印加試験による評価において、エッチングを行わなかった比較例の試料の場合、試験開始後短時間で絶縁抵抗の劣化が認められたが、この比較例に比べて、上述のエッチング液を用いてエッチングを行った本発明の実施例にかかる試料の場合には、絶縁抵抗が劣化するまでの時間が大幅に伸びており、十分な延命効果が得られることが確認された。   As shown in FIG. 2, in the evaluation by the underwater voltage application test, in the case of the sample of the comparative example in which etching was not performed, deterioration of the insulation resistance was recognized in a short time after the start of the test, but compared with this comparative example, In the case of the sample according to the example of the present invention etched using the above-described etching solution, it was confirmed that the time until the insulation resistance deteriorated greatly increased, and a sufficient life extension effect was obtained. It was.

めっき被膜の形成後にエッチングを行わない場合には、図３(ａ)に示すように、Ａｇ電極（外部電極本体）２ａの先端部（周縁部）が、Ｎｉめっき皮膜２ｂ、Ａｕめっき皮膜２ｃにより被覆されず、外部に露出しているため、Ａｇのマイグレーションにより絶縁抵抗の劣化を招いたものと考えられる。   When etching is not performed after the plating film is formed, as shown in FIG. 3A, the tip (peripheral edge) of the Ag electrode (external electrode body) 2a is formed by the Ni plating film 2b and the Au plating film 2c. Since it is not covered and exposed to the outside, it is considered that the deterioration of the insulation resistance was caused by the migration of Ag.

これに対し、めっき被膜の形成後にエッチングを行った場合には、めっき被膜２ｂ，２ｃの形成後の段階では、図３(ａ)に示すように、めっき皮膜２ｂ，２ｃにより被覆されずに外部に露出していたＡｇ電極（外部電極本体）２ａの先端部（周縁部）が、エッチングにより、図３(ｂ)（および図１(ｂ)）に示すように除去されて、Ａｇのマイグレーションが起こりにくくなったことによるものと考えられる。   On the other hand, when etching is performed after the formation of the plating film, in the stage after the formation of the plating films 2b and 2c, as shown in FIG. The tip (peripheral edge) of the Ag electrode (external electrode main body) 2a exposed in FIG. 3B is removed by etching as shown in FIG. 3B (and FIG. 1B), and Ag migration occurs. This is thought to be due to the fact that it is less likely to occur.

表３Ａ、表３Ｂに示すような組成を有するエッチング液１〜１９を用意した。
また、エッチング特性を調べるためのエッチング対象物（試料）として、
(ａ)Ｃｕ箔の表面にＮｉめっき皮膜を形成し、さらにＮｉめっき皮膜上にＡｕめっき皮膜を形成しためっき被膜付きＣｕ箔と、
(ｂ)無垢のＡｇ箔と
を用意した。 Etching liquids 1 to 19 having compositions as shown in Table 3A and Table 3B were prepared.
In addition, as an etching object (sample) for examining etching characteristics,
(a) a Cu foil with a plating film in which a Ni plating film is formed on the surface of the Cu foil, and an Au plating film is further formed on the Ni plating film;
(b) A solid Ag foil and

そして、上述のめっき被膜付きＣｕ箔と、Ａｇ箔とを、表３Ａ、表３Ｂのエッチング液１〜１９に浸漬し、めっき被膜付きＣｕ箔におけるめっき被膜（Ｎｉめっき皮膜とＡｕめっき皮膜）の腐食の進行の状態を観察するとともに、Ａｇ箔のエッチング（溶解）の進行状態を調べ、その結果から各エッチング液のＡｇ選択エッチング性を評価した。
その結果を表３Ａ、表３Ｂに併せて示す。 And the above-mentioned Cu foil with a plating film and Ag foil are immersed in the etching solutions 1-19 of Table 3A and Table 3B, and corrosion of the plating film (Ni plating film and Au plating film) in Cu foil with a plating film In addition to observing the progress of the etching, the progress of the etching (dissolution) of the Ag foil was examined, and the Ag selective etching property of each etching solution was evaluated from the results.
The results are also shown in Tables 3A and 3B.

Figure 0005621671
Figure 0005621671

Figure 0005621671
Figure 0005621671

なお、Ａｇ選択エッチング性を評価するにあたっては、めっき皮膜に腐食が認められず、Ａｇ箔のエッチングが進行した（Ａｇ箔が溶解した）エッチング液を、Ａｇ選択エッチング性が良好（○）であると評価した。   In evaluating the Ag selective etching property, the plating film was not corroded, and the etching solution in which the etching of the Ag foil progressed (the Ag foil was dissolved) had a good Ag selective etching property (◯). It was evaluated.

すなわち、めっき皮膜に腐食が認められたエッチング液は、Ａｇ箔のエッチングの進行の程度を問わず、Ａｇ選択エッチング性が不良（×）であると評価した。
また、Ａｇ箔のエッチングが進行しない（Ａｇ箔が溶解しない）か、Ａｇ箔のエッチングは進行するが、進行が遅い（Ａｇ箔は溶解するが、溶解が遅い）エッチング液は、めっき皮膜の腐食の程度を問わず、Ａｇ選択エッチング性が不良（×）であると評価した。 That is, the etching solution in which corrosion was observed in the plating film was evaluated as having poor (x) Ag selective etching property regardless of the progress of the etching of the Ag foil.
Etching of Ag foil does not progress (Ag foil does not dissolve) or Ag foil etching progresses but progresses slowly (Ag foil dissolves but dissolves slowly). Regardless of the degree, the Ag selective etching property was evaluated to be poor (x).

表３Ａ、３Ｂに示すように、
・エッチング液番号１１および１２のペルオキソ２硫酸アンモニウムの水溶液、
・エッチング液番号１４のアンモニアと過酸化水素の水溶液、
・エッチング液番号１５，１６の硫酸鉄（III）アンモニウムの水溶液、および、
・エッチング液番号１７の硝酸鉄（III）の水溶液
をエッチング液として用いた場合、Ａｇ選択エッチング性が良好（○）であることが確認された。 As shown in Tables 3A and 3B,
An aqueous solution of ammonium peroxodisulfate in etchants 11 and 12;
-Aqueous solution of ammonia and hydrogen peroxide with etching solution number 14
-An aqueous solution of ammonium (III) sulfate with etchant numbers 15 and 16, and
-When the aqueous solution of iron nitrate (III) with the etching solution number 17 was used as the etching solution, it was confirmed that the Ag selective etching property was good (◯).

また、Ａｇ選択エッチング性が良好（○）である上記のエッチング液番号１１，１２，１４，１５，１６，１７の各エッチング液は、いずれも、ｐＨが１．０以上でのエッチング液である。このように、ｐＨが１．０以上のエッチング液を用いることにより、Ｎｉめっき皮膜やＡｕめっき皮膜を腐食させることなく、Ａｇ電極を効率よく選択エッチングすることができて望ましい。   Moreover, each etching solution of said etching liquid number 11, 12, 14, 15, 16, 17 with favorable Ag selective etching property ((circle)) is an etching liquid in which pH is 1.0 or more. . Thus, by using an etching solution having a pH of 1.0 or more, it is desirable that the Ag electrode can be selectively etched efficiently without corroding the Ni plating film or the Au plating film.

上記の要件を満たす、本発明において用いることが可能なエッチング液の構成成分としては、表３Ｂのエッチング液番号１１，１２，１４，１５，１６，１７のエッチング液を構成する成分（構成材）以外にも、クエン酸鉄（III）、アセチルアセトナート鉄（III）、エチレンジアミン四酢酸−ナトリウム鉄（III）、リン酸鉄（III）、三シュウ酸三アンモニウム鉄（III）、次亜リン酸鉄（III）、二リン酸鉄（III）、シュウ酸鉄（III）、アクリル酸鉄（III）などが例示され、これらの成分を含むエッチング液を用いた場合も、上述の実施例の場合と同様の効果が得られるものと考えられる。   As the constituents of the etching solution that satisfies the above requirements and can be used in the present invention, the components (components) constituting the etching solutions of the etching numbers 11, 12, 14, 15, 16, and 17 in Table 3B. In addition, iron (III) citrate, iron (III) acetylacetonate, ethylenediaminetetraacetic acid-sodium iron (III), iron (III) phosphate, triammonium iron oxalate (III), hypophosphorous acid Examples include iron (III), iron (III) diphosphate, iron (III) oxalate, iron (III) acrylate, and the like in the case of the above-described embodiment even when an etching solution containing these components is used. It is considered that the same effect can be obtained.

上記実施例では、電子部品としてセラミック多層基板を製造する場合を例にとって説明したが、本発明は、電子部品素体の表面に、外部電極本体（Ａｇ電極）と、その表面に形成されたＮｉめっき皮膜とＡｕめっき皮膜とを備えた外部電極を有する種々の電子部品を製造する場合に広く適用することが可能である。   In the above embodiment, the case where a ceramic multilayer substrate is manufactured as an electronic component has been described as an example. However, the present invention provides an external electrode body (Ag electrode) and Ni formed on the surface of the electronic component element body. The present invention can be widely applied to the production of various electronic components having an external electrode provided with a plating film and an Au plating film.

また、本発明においては、Ａｇ電極のエッチングに用いられるエッチング液に種々の添加物を含有させることも可能であり、また、エッチング条件についても、上記実施例の条件に限定されるものではなく、電子部品に要求される特性などを考慮して、適切なエッチング条件を定めることが可能である。   Further, in the present invention, it is possible to contain various additives in the etching solution used for etching the Ag electrode, and the etching conditions are not limited to the conditions of the above embodiment, Appropriate etching conditions can be determined in consideration of characteristics required for electronic components.

本願発明は、さらにその他の点においても上記実施例に限定されるものではなく、外部電極本体の形成条件、ＮｉめっきやＡｕめっきの具体的な方法や条件などに関し、発明の範囲内において、種々の応用、変形を加えることが可能である。   The invention of the present application is not limited to the above-described embodiments in other respects as well, and it relates to the formation conditions of the external electrode body, specific methods and conditions of Ni plating and Au plating, etc. It is possible to add applications and modifications.

１ 内部導体
１ａ 配線
１ｂ ビアホール導体
２ 外部電極
２ａ 外部電極本体
２ｂ Ｎｉめっき皮膜
２ｃ Ａｕめっき皮膜
５ セラミック層
１０ セラミック多層基板本体
２０ 電子部品（セラミック多層基板） DESCRIPTION OF SYMBOLS 1 Internal conductor 1a Wiring 1b Via-hole conductor 2 External electrode 2a External electrode body 2b Ni plating film 2c Au plating film 5 Ceramic layer 10 Ceramic multilayer substrate body 20 Electronic component (ceramic multilayer substrate)

Claims (3)

電子部品素体と、その表面に形成された外部電極とを備えた電子部品の製造方法であって、
Ａｇを主成分とする材料からなる外部電極本体を形成する電極形成工程と、
前記外部電極本体の表面にＮｉめっき皮膜を形成し、その後に、前記Ｎｉめっき皮膜の表面にＡｕめっき皮膜を形成するめっき皮膜形成工程と、
前記めっき皮膜形成工程の後に、鉄（III）塩、過酸化水素、およびペルオキソ２硫酸アンモニウムからなる群より選ばれる少なくとも１種を含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、前記めっき皮膜から露出した前記外部電極本体の端部を除去するエッチング工程と
を備えていることを特徴とする電子部品の製造方法。 An electronic component manufacturing method comprising an electronic component element body and an external electrode formed on a surface thereof,
An electrode forming step of forming an external electrode body made of a material containing Ag as a main component;
Forming a Ni plating film on the surface of the external electrode body, and then forming a Au plating film on the surface of the Ni plating film; and
After the plating film forming step, etching is performed using an etching solution that contains at least one selected from the group consisting of iron (III) salt, hydrogen peroxide, and ammonium peroxodisulfate, and selectively dissolves Ag . And an etching process for removing an end portion of the external electrode body exposed from the plating film . 電子部品素体と、その表面に形成された外部電極とを備えた電子部品の製造方法であって、
Ａｇを主成分とする材料からなる外部電極本体を形成する電極形成工程と、
前記外部電極本体の表面にＮｉめっき皮膜を形成し、その後に、前記Ｎｉめっき皮膜の表面にＡｕめっき皮膜を形成するめっき皮膜形成工程と、
前記めっき皮膜形成工程の後に、硫酸鉄（III）アンモニウムを含み、Ａｇを選択的に溶解するエッチング液を用いてエッチングを行い、前記めっき皮膜から露出した前記外部電極本体の端部を除去するエッチング工程と
を備えていることを特徴とする電子部品の製造方法。 An electronic component manufacturing method comprising an electronic component element body and an external electrode formed on a surface thereof,
An electrode forming step of forming an external electrode body made of a material containing Ag as a main component;
Forming a Ni plating film on the surface of the external electrode body, and then forming a Au plating film on the surface of the Ni plating film; and
Etching using an etching solution containing iron (III) ammonium sulfate and selectively dissolving Ag after the plating film forming step to remove the end of the external electrode body exposed from the plating film An electronic component manufacturing method comprising: a process. 前記エッチング液として、ｐＨが１．０以上のものを用いることを特徴とする請求項１または２に記載の電子部品の製造方法。 The method for manufacturing an electronic component according to claim 1 , wherein the etchant has a pH of 1.0 or more.
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