JP2809030B2 - Surface structure of soldering member and surface treatment method of soldering member - Google Patents
Surface structure of soldering member and surface treatment method of soldering memberInfo
- Publication number
- JP2809030B2 JP2809030B2 JP3530893A JP3530893A JP2809030B2 JP 2809030 B2 JP2809030 B2 JP 2809030B2 JP 3530893 A JP3530893 A JP 3530893A JP 3530893 A JP3530893 A JP 3530893A JP 2809030 B2 JP2809030 B2 JP 2809030B2
- Authority
- JP
- Japan
- Prior art keywords
- soldering
- oxide film
- soldering member
- cleaning
- plating
- 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 - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面にニッケルめっき
が施された半田付け部材の表面構造および半田付け部材
の表面処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface structure of a soldering member having a surface plated with nickel and a method for treating a surface of the soldering member.
【０００２】[0002]
【従来の技術】従来、表面にニッケルめっき（以下、単
にＮｉめっきという）が施された半田付け部材は、図１
４に示すように構成されていた。2. Description of the Related Art Conventionally, a soldering member having a surface plated with nickel (hereinafter simply referred to as Ni plating) is shown in FIG.
4.
【０００３】図１４は従来のＮｉめっき式半田付け部材
を部分的に拡大して示す断面図である。同図において、
１は導電性材料からなる基材、２はこの基材１の表面に
設けられたＮｉめっき皮膜、３はＮｉめっき皮膜２の外
表面に形成された酸化膜である。FIG. 14 is a partially enlarged cross-sectional view showing a conventional Ni-plated soldering member. In the figure,
1 is a substrate made of a conductive material, 2 is a Ni plating film provided on the surface of the substrate 1, and 3 is an oxide film formed on the outer surface of the Ni plating film 2.
【０００４】この半田付け部材を製造する手順を図１５
によって説明する。図１５は従来から一般的に行われて
いるＮｉめっき方法の一例を示す工程図である。先ず、
基材１の表面に付着している油等を落とす（ステップＳ
１およびステップＳ２）。次に、基材１の表面に形成さ
れた酸化膜を取り除き、清浄な金属表面を露出させる
（ステップＳ３およびステップＳ４）。この後、電気め
っきや無電解めっきにより基材１の被めっき面に金属
（Ｎｉ）を析出させる（ステップＳ５）。そして、めっ
き材を洗浄する（ステップＳ６）ことにより、Ｎｉめっ
き表面からＮｉめっき液等を完全に除去した後、表面を
乾燥させる（ステップＳ７）。FIG. 15 shows a procedure for manufacturing this soldering member.
It will be explained by. FIG. 15 is a process chart showing an example of a conventional Ni plating method generally performed. First,
Drop oil or the like adhering to the surface of the substrate 1 (step S
1 and step S2). Next, the oxide film formed on the surface of the substrate 1 is removed to expose a clean metal surface (Steps S3 and S4). Thereafter, metal (Ni) is deposited on the surface of the substrate 1 to be plated by electroplating or electroless plating (step S5). Then, the plating material is washed (Step S6) to completely remove the Ni plating solution and the like from the Ni plating surface, and then the surface is dried (Step S7).
【０００５】前記ステップＳ６での洗浄は図１６に示す
ように行われる。図１６はＮｉめっき法におけるめっき
材の洗浄方法を示す構成図である。同図において、４は
洗浄容器、５はこの洗浄容器４に溜められた洗浄水であ
る。洗浄は、Ｎｉめっき皮膜２で表面が覆われた基材１
を洗浄水５中に浸漬させて行われる。The cleaning in step S6 is performed as shown in FIG. FIG. 16 is a configuration diagram showing a method of cleaning a plating material in the Ni plating method. In the figure, reference numeral 4 denotes a cleaning container, and 5 denotes cleaning water stored in the cleaning container 4. Cleaning is performed on the base material 1 whose surface is covered with the Ni plating film 2.
Is immersed in the washing water 5.
【０００６】このような金属析出直後の洗浄工程では、
めっき表面に洗浄水５による染みなどが残らないように
洗浄水５を速く乾燥させるため、洗浄水５の温度を高く
する傾向がある。しかし、洗浄水５をあまり高温にする
とその蒸発量も多くなるので、７０℃前後の温度が多く
採用されている。そして、洗浄水５はその熱伝達係数が
高いため、Ｎｉめっきされた基材１は数秒でその洗浄温
度に達し、その後基材１は洗浄水５から引き出して速や
かに乾燥する。In such a cleaning step immediately after metal deposition,
The temperature of the cleaning water 5 tends to be high in order to quickly dry the cleaning water 5 so that no stain or the like due to the cleaning water 5 remains on the plating surface. However, if the temperature of the cleaning water 5 is too high, the amount of evaporation increases, so that a temperature around 70 ° C. is often used. Since the cleaning water 5 has a high heat transfer coefficient, the Ni-plated substrate 1 reaches the cleaning temperature in a few seconds, and then the substrate 1 is pulled out from the cleaning water 5 and quickly dried. I do.
【０００７】すなわち、従来では、半田付け部材の表面
に生成される酸化膜３の構造、厚さおおび組成は制御さ
れていなかった。このため、Ｎｉめっき部分を半田付け
するときの半田ぬれ性は制御されておらず、半田付け箇
所を限定できるものではなかった。また、一般的にＮｉ
めっき式半田付け部材では半田ぬれ性は高くはなかっ
た。That is, conventionally, the structure, thickness and composition of the oxide film 3 formed on the surface of the soldering member have not been controlled. For this reason, the solder wettability when soldering the Ni-plated portion is not controlled, and the soldering location cannot be limited. In general, Ni
The plating type soldering members did not have high solder wettability.
【０００８】[0008]
【発明が解決しようとする課題】上述したように形成さ
れた半田付け部材を半田付けした場合、半田付け箇所
（接合面積）が安定せず、しかも、半田不ぬれ等の半田
付け不良も多発していた。また、半田付け部の信頼性も
著しく乏しかった。半田付け部材の半田付け例を図１７
に示す。When the soldering member formed as described above is soldered, a soldering portion (joining area) is not stable, and soldering failure such as non-wetting of the solder occurs frequently. I was Also, the reliability of the soldered portion was extremely poor. FIG. 17 shows an example of soldering of a soldering member.
Shown in
【０００９】図１７は従来の半田付け部材を半田付けし
たときの半田付け部を拡大して示す断面図で、同図
（ａ）は半田付け不良の状態を示し、同図（ｂ）は半田
付け良好の状態を示す。なお、Ｎｉめっき上の酸化膜は
省略して描いてある。同図において６は半田である。半
田付け良好である場合には同図（ｂ）に示すように半田
６は半田付け部分にぬれ広がっているが、半田付け不良
である場合には同図（ａ）に示すように接合面積が比較
的狭くなっている。FIG. 17 is an enlarged sectional view showing a soldering portion when a conventional soldering member is soldered. FIG. 17A shows a state of poor soldering, and FIG. This shows a good state of attachment. Note that the oxide film on the Ni plating is omitted. In the figure, reference numeral 6 denotes solder. When the soldering is good, the solder 6 spreads over the soldered portion as shown in FIG. 5B, but when the soldering is poor, the bonding area is reduced as shown in FIG. It is relatively narrow.
【００１０】従来では、一般的にＮｉめっき表面が半田
ぬれ性に乏しいため、Ｎｉめっき表面に、半田がぬれ広
がり易いＡｕ、Ａｇ等のめっきを施したり、半田付け前
に表面の酸化物を取り除く手法が採られていた。例え
ば、特開昭５９−５６９７２号公報に示された従来の半
田ぬれ性改良方法では、半田付け前に次亜リン酸ソーダ
に浸漬させることにより、Ｎｉめっきの表面に形成され
た酸化皮膜を除去し、半田付け性を向上させている。Conventionally, since the Ni plating surface generally has poor solder wettability, the Ni plating surface is plated with Au, Ag, or the like, which easily spreads solder, or oxides on the surface are removed before soldering. The technique was adopted. For example, in the conventional solder wettability improving method disclosed in Japanese Patent Application Laid-Open No. 59-56972, an oxide film formed on the surface of Ni plating is removed by immersion in sodium hypophosphite before soldering. And improves the solderability.
【００１１】ところが、この手法では、余分な工程が一
つ増えるばかりか、この液に電子部品等を漬けることは
できないので、半田付け部材に電子部品等が既に組み込
まれている場合には適用できない。また、上述したよう
に半田付け箇所にＡｕ、Ａｇ等をめっきする手法を採る
と、半田ぬれ性は改善されるもののコストが高くなると
いう問題が生じる。However, this method not only adds one extra step, but also cannot immerse the electronic components and the like in this liquid, so that it cannot be applied when the electronic components and the like are already incorporated in the soldering member. . As described above, when a method of plating Au, Ag, or the like on the soldered portion is employed, there is a problem that the solder wettability is improved but the cost is increased.
【００１２】本発明は上述したような問題点を解消する
ためになされたもので、半田ぬれ性の高いＮｉめっき表
面を局所的に設けて半田付け箇所を限定できる半田付け
部材を得ることを目的としており、さらに、そのような
半田付け部材を得るための表面処理方法を提供すること
を目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a soldering member capable of locally providing a Ni-plated surface having high solder wettability and limiting a soldering position. It is another object of the present invention to provide a surface treatment method for obtaining such a soldering member.
【００１３】[0013]
【課題を解決するための手段】第１の発明に係る半田付
け部材の表面構造は、ニッケルめっき部分の表面に生成
される酸化膜を、半田付け部位では非晶質とし、非半田
付け部位では結晶質としたものである。According to a first aspect of the present invention, a surface structure of a soldering member is such that an oxide film formed on a surface of a nickel plating portion is made amorphous at a soldering portion, and is made amorphous at a non-soldering portion. It was made crystalline.
【００１４】第２の発明に係る半田付け部材の表面構造
は、表面にニッケルめっきが施された半田付け部材の表
面構造において、ニッケルめっき部分の表面に生成され
る酸化膜を、半田付け部位では膜厚を比較的薄く形成
し、非半田付け部位では前記半田付け部位より膜厚を厚
く形成したものである。[0014] The surface structure of the soldering member according to the second aspect of the present invention is the surface structure of a soldering member having a surface plated with nickel, wherein an oxide film formed on the surface of the nickel-plated portion is covered with an oxide film at the soldering portion. The film thickness is formed relatively thin, and the film thickness is formed thicker at the non-soldered portion than at the soldered portion.
【００１５】第３の発明に係る半田付け部材の表面処理
方法は、第１の発明または第２の発明の酸化膜を、ニッ
ケルめっき後に半田付け部材を洗浄するときに、半田付
け部位を略４０℃以下の温度の洗浄液によって洗浄し、
非半田付け部位を前記温度より十分に高い温度の洗浄液
によって洗浄して成膜させるものである。According to a third aspect of the present invention, there is provided a method for treating a surface of a soldering member according to the first or second aspect of the present invention. Washing with a washing solution at a temperature of ℃ or less,
The non-soldering portion is cleaned with a cleaning liquid at a temperature sufficiently higher than the above temperature to form a film.
【００１６】第４の発明に係る半田付け部材の表面処理
方法は、半田付け部材の表面にニッケルめっきを施した
後、この半田付け部材を略４０℃以下の温度の洗浄液に
浸漬させ、この状態で非半田付け部位にエネルギービー
ムを照射して非半田付け部位を前記温度より十分に高い
温度に高めるものである。According to a fourth aspect of the present invention, there is provided a method for treating a surface of a soldering member, wherein after the surface of the soldering member is plated with nickel, the soldering member is immersed in a cleaning liquid at a temperature of about 40 ° C. or less. Then, the non-soldered portion is irradiated with an energy beam to raise the non-soldered portion to a temperature sufficiently higher than the above temperature.
【００１７】第５の発明に係る半田付け部材の表面処理
方法は、半田付け部材の表面にニッケルめっきを施した
後、この半田付け部材を洗浄するときに、半田付け部位
を略４０℃以下の温度のアルコール系洗浄液によって洗
浄して半田付け部位に半田ぬれ性が高い組成の酸化膜を
成膜させ、非半田付け部位を前記温度より十分に高い温
度の洗浄液によって洗浄して非半田付け部位に前記酸化
膜より半田ぬれ性が低い組成の酸化膜を成膜させるもの
である。According to a fifth aspect of the present invention, there is provided a method for treating a surface of a soldering member, wherein after the surface of the soldering member is subjected to nickel plating, when the soldering member is washed, the soldering portion is kept at approximately 40 ° C. or lower. Cleaning with an alcohol-based cleaning solution at a temperature to form an oxide film having a high solder wettability on the soldered portion, and cleaning the non-soldered portion with a cleaning solution having a temperature sufficiently higher than the above temperature to form a non-soldered portion on the non-soldered portion. An oxide film having a composition lower in solder wettability than the oxide film is formed.
【００１８】[0018]
【作用】本発明に係る半田付け部材は、半田付け部位で
半田がぬれ易く、それ以外の部位は半田がぬれ難くな
る。In the soldering member according to the present invention, the solder is easily wetted at the soldered portion, and the solder is hardly wetted at other portions.
【００１９】[0019]
【実施例】発明者らは、Ｎｉめっきの半田付け性の劣化
の原因がめっき後の保管状態による経時変化（表面酸
化）ではないということを発見した。これは、昨今の品
質管理技術の向上により、Ｎｉめっきの品質はめっき後
には殆ど経時変化することなく確保されているからであ
る。さらに、種々の環境加速試験によっても、半田付け
性はさほど変化せず、結局、Ｎｉめっきの半田付け性は
めっき方法、特に金属析出後の洗浄方法に大きく依存し
ていることを発見した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The inventors have found that the cause of the deterioration of the solderability of Ni plating is not the change over time (surface oxidation) due to the storage state after plating. This is because the quality of Ni plating is secured with little change over time after plating due to recent improvements in quality control technology. Furthermore, it has been found that the solderability does not change so much by various environmental acceleration tests, and that the solderability of Ni plating largely depends on the plating method, particularly the cleaning method after metal deposition.
【００２０】そこで、半田付け部材の半田付け部位を、
Ｎｉめっきの金属析出後の洗浄方法に工夫を凝らすこと
によって、半田がぬれ易くした。言い換えれば、洗浄を
以下に述べるように行い、半田付け部材のめっき表面に
生成される酸化膜の結晶構造、膜厚、組成を変えること
によって、半田がぬれ易くなることを見出したのであ
る。以下、酸化膜の結晶構造、膜厚、組成を変えて半田
ぬれ性を高める技術をそれぞれ第１、第２、第５の発明
として説明する。なお、第３および第４の発明は第１，
第２の発明に係る酸化膜を成膜させるための表面処理方
法である。Therefore, the soldering portion of the soldering member is
The solder was easily wetted by devising a cleaning method after the metal deposition of Ni plating. In other words, it has been found that the solder is easily wetted by performing cleaning as described below and changing the crystal structure, film thickness, and composition of the oxide film formed on the plating surface of the soldering member. Hereinafter, techniques for improving the solder wettability by changing the crystal structure, film thickness, and composition of the oxide film will be described as first, second, and fifth inventions, respectively. The third and fourth inventions are the first and fourth inventions.
This is a surface treatment method for forming an oxide film according to the second invention.
【００２１】（１）第１の発明に係る半田付け部材の表
面構造について 実施例１．第１の発明に係る半田付け部材の表面構造を
図１ないし図３によって詳細に説明する。図１は洗浄水
温度とＮｉめっき表面の酸化膜の結晶構造との関係を示
すＲＨＥＥＤ分析結果の模式図、図２は第１の発明に係
る半田付け部材の要部を拡大して示す断面図である。図
３は第１の発明に係る半田付け部材を形成するための製
造方法を示す図で、同図（ａ）は半田付け部位を洗浄し
ている状態を示し、同図（ｂ）は非半田付け部位を洗浄
している状態を示す。(1) Surface Structure of Soldering Member According to First Embodiment The surface structure of the soldering member according to the first invention will be described in detail with reference to FIGS. FIG. 1 is a schematic diagram of RHEED analysis results showing a relationship between a cleaning water temperature and a crystal structure of an oxide film on a Ni plating surface, and FIG. 2 is a cross-sectional view showing an enlarged main part of a soldering member according to the first invention. It is. 3A and 3B are views showing a manufacturing method for forming a soldering member according to the first invention. FIG. 3A shows a state in which a soldering part is being cleaned, and FIG. This shows a state in which the attachment site is being cleaned.
【００２２】図１は、Ｎｉめっき過程での金属析出後の
洗浄工程において、半田付け部材を水中に３０秒間浸漬
させることによりＮｉめっき表面に形成された酸化膜の
構造をＲＨＥＥＤ（反射高速電子回析）で分析した結果
を示す図である。同図において、（ａ）図は２０℃の洗
浄水を用いた場合を示し、（ｂ）図は４０℃の洗浄水を
用いた場合を示し、（ｃ）図は５０℃の洗浄水を用いた
場合を示し、（ｄ）図は８０℃の洗浄水を用いた場合を
示し、（ｅ）図は９５℃の洗浄水を用いた場合を示す。FIG. 1 shows that the structure of the oxide film formed on the Ni plating surface by immersing the soldering member in water for 30 seconds in a cleaning step after the metal deposition in the Ni plating process is RHEED (reflection high-speed electron recovery). It is a figure which shows the result analyzed by (analysis). In the same figure, (a) shows a case using 20 ° C. washing water, (b) shows a case using 40 ° C. washing water, and (c) shows a case using 50 ° C. washing water. (D) shows the case where the washing water at 80 ° C. is used, and (e) shows the case where the washing water at 95 ° C. is used.
【００２３】図１に示すように、洗浄水温度が４０℃以
下の場合には、Ｎｉめっき表面に生成される酸化膜の構
造はアモルファス（非晶質）に近く、５０℃以上では結
晶質となる。As shown in FIG. 1, when the temperature of the cleaning water is 40 ° C. or lower, the structure of the oxide film formed on the Ni plating surface is close to amorphous (amorphous). Become.
【００２４】発明者らは、これらの結晶構造の違いによ
り半田ぬれ性が著しく異なり、酸化膜の結晶構造がアモ
ルファスである場合には半田ぬれ性が高く、一方、結晶
質の場合では半田ぬれ性が低いことを発見した。そこ
で、半田付け部位の酸化膜の結晶構造をアモルファスに
し、それ以外の非半田付け部位の酸化膜の結晶構造を結
晶質とすることによって、半田付け箇所を限定するよう
にした。半田付けは、半田付け操作時間内に被半田付け
接続部分の表面が半田でぬれ、その後にディウェッティ
ングを生じないことが重要である。すなわち、被半田付
け接続部分は、ぬれ性の高い（絶対値）方がよいことは
いうまでもない。 本明細書で用いる「半田ぬれ性が高い
とか低い」という表現は、同じ半田付け条件下での相対
的な比較をしており、半田のぬれ時間や最終的な半田の
広がりの相対的な違いから判断するものである。 なお、
この判断基準としては、半田のぬれに伴って生じる表面
張力を利用して測定するメニスコグラフ法がある。 The inventors have found that the solder wettability differs significantly due to the difference in these crystal structures. When the oxide film has an amorphous crystal structure, the solder wettability is high. On the other hand, when the oxide film is crystalline, the solder wettability is high. Was found to be low. In view of this, the soldering portion is limited by making the crystal structure of the oxide film at the soldering portion amorphous and making the crystal structure of the oxide film at the other non-soldering portion crystalline. Soldering is performed within the soldering operation time
The surface of the connection is wet with solder and then
It is important not to cause aging. That is,
It is better that the connection part should have high wettability (absolute value).
Needless to say. "High solder wettability" used in this specification
The expression "low" is a relative value under the same soldering conditions.
Comparison of the solder wetting time and final solder
Judgment is made based on the relative difference in spread. In addition,
This criterion is based on the surface generated by solder wetting.
There is a meniscograph method in which measurement is performed using tension.
【００２５】以下、上述したように酸化膜の結晶構造を
変えた実施例について説明する。図２において、符号１
は半田付け部材の基材、２はこの基材１の表面に施され
たＮｉめっき皮膜、３はこのＮｉめっき皮膜２の表面に
生成された酸化膜である。また、ＷはＮｉめっき処理が
施された半田付け部材を示す。Hereinafter, an embodiment in which the crystal structure of the oxide film is changed as described above will be described. In FIG.
Is a substrate of the soldering member, 2 is a Ni plating film applied to the surface of the substrate 1, and 3 is an oxide film formed on the surface of the Ni plating film 2. W indicates a soldering member on which a Ni plating process has been performed.
【００２６】この酸化膜３は、結晶構造がアモルファス
であるアモルファス酸化膜３ａと、結晶構造が結晶質で
ある結晶質酸化膜３ｂとから構成されている。そして、
前記アモルファス酸化膜３ａは半田付けされる部位（半
田付け部位２ａ）に形成され、結晶質酸化膜３ｂは半田
付けされない部位（非半田付け部位２ｂ）に形成されて
いる。The oxide film 3 includes an amorphous oxide film 3a having an amorphous crystal structure and a crystalline oxide film 3b having a crystalline crystal structure. And
The amorphous oxide film 3a is formed at a portion to be soldered (soldering portion 2a), and the crystalline oxide film 3b is formed at a portion not to be soldered (non-soldering portion 2b).
【００２７】このように半田付け部材の表面に異なる構
造の酸化膜３（アモルファス酸化膜３ａおよび結晶質酸
化膜３ｂ）を形成したことによって、半田のぬれ性を制
御でき、半田付け部位を限定することができる。このた
め、半田付け接合部の形状が安定し、半田付け部の信頼
性が向上する。半田ぬれ性には、めっき表面の酸化膜の
構造・膜厚・組成が大きく影響する。図２は、異なる酸
化膜構造を特に強調した図であり、膜厚の情報は省略し
てある。 Since the oxide films 3 (amorphous oxide film 3a and crystalline oxide film 3b) having different structures are formed on the surface of the soldering member as described above, the wettability of the solder can be controlled, and the soldering portion is limited. be able to. For this reason, the shape of the solder joint is stabilized, and the reliability of the solder joint is improved. The solder wettability depends on the oxide film on the plating surface.
The structure, film thickness, and composition have a significant effect. Figure 2 shows different acids
This figure emphasizes the oxide film structure, and the thickness information is omitted.
It is.
【００２８】実施例２．上述した酸化膜３は図３に示す
ようにして成膜させる。なお、この成膜方法は、第３の
発明に係る表面処理方法を構成している。図３におい
て、１１および１２は洗浄水である。洗浄水１１は５℃
の脱イオン水、洗浄水１２は９０℃の脱イオン水であ
る。これらの洗浄水１１，１２中に電気Ｎｉめっきで金
属（Ｎｉ）を析出させた半田付け部材Ｗを没入させて３
０秒間洗浄する。Embodiment 2 FIG. The above-described oxide film 3 is formed as shown in FIG. This film forming method constitutes the surface treatment method according to the third invention. In FIG. 3, reference numerals 11 and 12 denote washing water. Washing water 11 is 5 ° C
The deionized water and washing water 12 are 90 ° C. deionized water. The soldering member W, on which metal (Ni) is deposited by electric Ni plating, is immersed in these cleaning waters 11 and 12 to remove
Wash for 0 seconds.
【００２９】このとき、半田付け部位（図中２ａで示
す）は洗浄水１１によって洗浄し、非半田付け部位（図
中２ｂで示す）は洗浄水１２によって洗浄する。このよ
うに洗浄を行うことによって図２に示した構造の酸化膜
３が成膜される。At this time, the soldering portion (indicated by 2a in the figure) is cleaned with the cleaning water 11, and the non-soldering portion (indicated by 2b in the drawing) is cleaned with cleaning water 12. By performing such cleaning, the oxide film 3 having the structure shown in FIG. 2 is formed.
【００３０】なお、電気Ｎｉめっきは以下のようにして
行った。 硫酸ニッケル（ＮｉＳＯ4・６Ｈ2Ｏ）→２４０ｇ／ｌ 塩化ニッケル（ＮｉＣｌ2・６Ｈ2Ｏ）→４５ｇ／ｌ ほう酸 （Ｈ3ＢＯ3） →３５ｇ／ｌ の標準的なワット浴に市販の光沢剤を適量混入させ、ｐ
Ｈ＝４に調整しためっき液を使用し、浴温５０℃、電流
密度４Ａ／ｄｍ2 で空気攪拌しながら行った。The electric Ni plating was performed as follows. Commercial brightener standard Watts bath nickel sulfate (NiSO 4 · 6H 2 O) → 240g / l nickel chloride (NiCl 2 · 6H 2 O) → 45g / l boric acid (H 3 BO 3) → 35g / l Mixed in an appropriate amount, and p
Using a plating solution adjusted to H = 4, a bath temperature of 50 ° C. and a current density of 4 A / dm 2 were performed while stirring with air.
【００３１】実施例３．上記実施例ではアモルファスの
酸化膜を生成させるために５℃の脱イオン水を用いた
が、水温は４０℃以下であれば何度でもよく、０℃以下
でもよい。また、洗浄水は脱イオン水に限られることな
く、蒸留水や水道水を使用することもできる。さらに、
完全に液体である必要もなく、氷等の固体を含んでいて
もよい。加えて、洗浄時間としては３０秒に限らないと
いうことはいうまでもない。Embodiment 3 FIG. In the above embodiment, deionized water at 5 ° C. was used to form an amorphous oxide film. However, the water temperature may be any number as long as it is 40 ° C. or less, or may be 0 ° C. or less. Further, the washing water is not limited to deionized water, and distilled water or tap water can also be used. further,
It does not need to be completely liquid, and may contain a solid such as ice. In addition, it goes without saying that the cleaning time is not limited to 30 seconds.
【００３２】実施例４．上記実施例では結晶質の酸化膜
を生成させるために９０℃の脱イオン水を用いたが、水
温は５０℃以上であれば何度でもよく、１００℃以上で
もよい。また、洗浄水は脱イオン水に限らず、蒸留水や
水道水でもよい。また、液体に限られることなく、水蒸
気でもよい。加えて、洗浄時間は３０秒に限らないとい
うことはいうまでもない。Embodiment 4 FIG. In the above embodiment, deionized water of 90 ° C. was used in order to form a crystalline oxide film, but the water temperature may be any number as long as it is 50 ° C. or more, and may be 100 ° C. or more. Further, the washing water is not limited to deionized water, but may be distilled water or tap water. In addition, water vapor may be used without being limited to liquid. In addition, it goes without saying that the cleaning time is not limited to 30 seconds.
【００３３】（２）第２の発明に係る半田付け部材の表
面構造について 実施例５． 第２の発明に係る半田付け部材の表面構造を図４〜図７
によって説明する。図４は洗浄水に半田付け部材を３０
秒間浸漬させた場合の洗浄水温度と酸化膜の膜厚との関
係を示すグラフ、図５は第２の発明に係る半田付け部材
の要部を拡大して示す断面図、図６は洗浄水として６０
℃の脱イオン水を使用したときの洗浄時間と酸化膜の膜
厚との関係を示すグラフ、図７は第２の発明に係る半田
付け部材を形成するための製造方法を示す図で、同図
（ａ）は半田付け部位を洗浄している状態を示し、同図
（ｂ）は非半田付け部位を洗浄している状態を示す。こ
れらの図において前記図１ないし図３で説明したものと
同一もしくは同等部材については、同一符号を付し詳細
な説明は省略する。(2) Surface Structure of Soldering Member According to Second Embodiment FIGS. 4 to 7 show the surface structure of the soldering member according to the second invention.
It will be explained by. FIG. 4 shows that 30 parts of the soldering member are
FIG. 5 is a graph showing the relationship between the temperature of the cleaning water and the thickness of the oxide film when immersed for 2 seconds, FIG. 5 is a cross-sectional view showing an enlarged main part of the soldering member according to the second invention, and FIG. As 60
FIG. 7 is a graph showing the relationship between the cleaning time and the thickness of the oxide film when using deionized water at ° C. FIG. 7 is a view showing a manufacturing method for forming a soldering member according to the second invention. FIG. 7A shows a state where a soldering part is being cleaned, and FIG. 7B shows a state where a non-soldering part is being cleaned. In these drawings, the same or equivalent members as those described in FIGS. 1 to 3 are denoted by the same reference numerals, and detailed description is omitted.
【００３４】図４は金属析出後の洗浄工程において、半
田付け部材を洗浄水中に３０秒浸漬させた場合の洗浄水
温度と、Ｎｉめっき表面に形成された酸化膜の厚みとの
関係を示すグラフである。同図に示すように、洗浄条件
によって酸化膜厚を制御でき、洗浄水温度を５０℃以下
にすることで酸化膜を薄くすることができる。FIG. 4 is a graph showing the relationship between the temperature of the cleaning water when the soldering member is immersed in the cleaning water for 30 seconds and the thickness of the oxide film formed on the Ni plating surface in the cleaning step after the metal deposition. It is. As shown in the figure, the oxide film thickness can be controlled by the cleaning conditions, and the oxide film can be thinned by setting the temperature of the cleaning water to 50 ° C. or lower.
【００３５】発明者らは、この酸化膜の膜厚の違いによ
り半田ぬれ性が著しく異なり、酸化膜厚が薄い場合には
半田ぬれ性が高く、酸化膜厚が厚い場合には半田ぬれ性
が低くなることを発見した。また、酸化膜の厚みが５ｎ
ｍ以上異なりさえすれば半田ぬれ性を充分に制御できる
ことが判明した。そこで、半田付け部位の酸化膜を非半
田付け部位の酸化膜より薄くすることによって、半田付
け箇所を限定するようにした。The inventors remarkably differ in the solder wettability due to the difference in the thickness of the oxide film. The solder wettability is high when the oxide film is thin, and the solder wettability is high when the oxide film is thick. I found it to be lower. The thickness of the oxide film is 5n.
It has been found that the solder wettability can be sufficiently controlled if the difference is at least m. Therefore, the soldering portion is limited by making the oxide film at the soldering portion thinner than the oxide film at the non-soldering portion.
【００３６】図５において、３ｃは膜厚が薄い酸化膜、
３ｄは膜厚が厚い酸化膜である。これらの酸化膜３ｃ，
３ｄは膜厚が５ｎｍ以上異なっている。そして、薄い酸
化膜３ｃは半田付け部位２ａに形成され、厚い酸化膜３
ｄは非半田付け部位２ｂに形成されている。In FIG. 5, 3c is a thin oxide film,
3d is a thick oxide film. These oxide films 3c,
3d differs in film thickness by 5 nm or more. Then, the thin oxide film 3c is formed at the soldering portion 2a, and the thick oxide film 3c is formed.
d is formed in the non-soldering portion 2b.
【００３７】このように半田付け部材Ｗの表面に膜厚の
異なる酸化膜３ｃ，３ｄを形成したことにより、半田の
ぬれ性を制御できる。すなわち、レジスト等を用いるこ
となく半田付け箇所を限定でき、半田付け接合部の形状
が安定し、半田付け部の信頼性が向上する。ここで、酸
化膜３ｃ，３ｄの膜厚が５ｎｍ以上異なることにより半
田のぬれ性を制御できることの理由についてさらに詳細
に説明する。 極端な例として、半田ぬれ性の極めて差の
ある酸化膜を形成した場合であっても、強活性のフラッ
クスを用いて高温で長時間半田付けすると、相対的に半
田ぬれ性の低い箇所まで半田がぬれてしまい、半田付け
部材のぬれを制御することはできない。一方、フラック
スレスで低温かつ短時間の半田付けでは、相対的に半田
ぬれ性の高い箇所さえ半田をぬらすことはできず、半田
付け部材のぬれを制御することはできない。すなわち、
相対的に半田ぬれ性の高い箇所のみで半田がぬれ、相対
的に半田ぬれ性の低い箇所は半田がぬれないように、半
田付け時に用いるフラックスや、半田付け時の雰囲気、
半田付けの加熱プロファイルなどを選択する必要があ
る。 酸化膜の膜厚については、膜厚差が大きければ大き
い程、相対的な半田ぬれ性の差が十分確保できるため、
半田付け部材の半田のぬれの制御（相対的に半田ぬれ性
の高い箇所のみを半田でぬらすこと）が容易となる。す
なわち、この実施例においては、膜厚差が５ｎｍ以上あ
ればフラックスの活性度や半田付け加熱プロファイルな
どの選択を容易に行うことができ、半田のぬれを制御
（相対的に半田ぬれ性の高い箇所のみを半田でぬらすこ
と）できることを確認したということである。 酸化膜の
表面粗さは酸化膜が非常に薄いため、下地（めっき膜）
の表面粗さに大きく依存する。しかし、Ｒｍａｘ０．１
μｍの光沢ニッケルめっきでも、実際に洗浄条件によっ
て酸化膜厚は制御可能である。 酸化膜は、上述した実施
例１で説明したように、非晶質のものより結晶質のもの
の方が半田ぬれ性が低い。同じ構造の酸化膜では、厚み
が厚い方がぬれ性が低い。この半田ぬれ性の差を利用し
て相対的に半田ぬれ性の高い箇所と低い箇所を 設けるこ
とがポイントである。よって、相対的に結晶質酸化膜で
も、酸化膜厚差の異なる表面を形成することで、半田の
ぬれを制御（相対的に半田ぬれ性の高い箇所のみを半田
でぬらすこと）することができる。具体的に図５に示し
た酸化膜は、相対的に半田ぬれ性の高い箇所も結晶質酸
化膜なので、少し活性力の強めのフラックスを用いるこ
となどによって、半田付け部材のぬれを制御することが
できる。 By forming the oxide films 3c and 3d having different thicknesses on the surface of the soldering member W, the wettability of the solder can be controlled. That is, the soldering portion can be limited without using a resist or the like, the shape of the soldering joint is stabilized, and the reliability of the soldering portion is improved. Where the acid
When the thicknesses of the oxide films 3c and 3d differ by 5 nm or more, half
More details on why we can control the wettability of the fields
Will be described. An extreme example is the extreme difference in solder wettability.
Even if a certain oxide film is formed, a strongly active flash
When soldering at high temperature for a long time using
Solder gets wet to the low wettability and soldering
It is not possible to control the wetting of the members. Meanwhile, Flack
For low-temperature, short-time soldering with a thin solder,
Even wet parts cannot wet the solder.
It is not possible to control the wetting of the attachment members. That is,
Solder is wet only at relatively high solder wettability,
In places with low solder wettability, make sure that the solder is not wet.
The flux used during padding, the atmosphere used during soldering,
It is necessary to select a soldering heating profile, etc.
You. Regarding the thickness of the oxide film, the larger the difference in film thickness, the larger
Since the difference in relative solder wettability can be sufficiently secured,
Control of solder wettability of soldering members (relative solder wettability)
(Wet only the high places with the solder)). You
That is, in this embodiment, the difference in film thickness is 5 nm or more.
Flux activity and soldering heating profile
Which choice can be easily made and control solder wetting
(Wet only parts with relatively high solder wettability with solder.
And) that you can do it. Oxide film
The surface roughness of the oxide film is very thin, so the underlayer (plating film)
Greatly depends on the surface roughness. However, Rmax0.1
Even bright nickel plating of μm depends on the actual cleaning conditions.
Thus, the oxide film thickness can be controlled. The oxide film is formed as described above.
As described in Example 1, a crystalline material is more crystalline than an amorphous material
Has lower solder wettability. For an oxide film of the same structure,
The thicker, the lower the wettability. Utilizing this difference in solder wettability
It is necessary to provide relatively high and low solder wettability
Is the point. Therefore, a relatively crystalline oxide film
Also, by forming surfaces with different oxide film thickness differences,
Wetting control (only soldering with relatively high solder wettability)
Wet). Specifically shown in FIG.
The oxide film that has relatively high solder wettability
Use a slightly more active flux.
It is possible to control the wetting of the soldering member by
it can.
【００３８】実施例６． 上述した膜厚の異なる酸化膜３ｃ，３ｄを成膜させる手
法を図６および図７によって説明する。図６は６０℃の
洗浄水を使用したときの洗浄時間と酸化膜厚の関係を示
すグラフで、同図から分かるように、時間と共に酸化膜
厚が増大している。そこで、図７に示したように、半田
付け部位２ａを６０℃の脱イオン水１３中に３０秒間没
入させ、非半田付け部位２ｂを同じ脱イオン水１３に１
２０秒間没入させる。このように洗浄を行うことによっ
て図５に示した膜厚の酸化膜３ｃ，３ｄが成膜される。
なお、前記図４と図６とで、めっき後の洗浄条件が同じ
条件の下で、酸化膜厚が異なっているのは、図４と図６
とで実験に用いためっき膜の膜厚が異なっているからで
ある。めっき膜厚が異なると、めっき膜の構造や不純物
の含有量が異なってくるため、その上に形成される酸化
膜は、洗浄条件が同じでも異なるからである。ちなみ
に、めっき膜はめっき時のめっき浴温や電流密度などの
めっき条件や、めっき浴組成の違い、光沢剤などの添加
剤の種類や添加量によっても変わる。 Embodiment 6 FIG. A method for forming the oxide films 3c and 3d having different thicknesses will be described with reference to FIGS. FIG. 6 is a graph showing the relationship between the cleaning time and the oxide film thickness when the cleaning water at 60 ° C. is used. As can be seen from FIG. 6, the oxide film thickness increases with time. Therefore, as shown in FIG. 7, the soldering part 2a is immersed in deionized water 13 at 60 ° C. for 30 seconds, and the non-soldering part 2b is placed in the same deionized water 13 for one second.
Immerse for 20 seconds. By performing such cleaning, the oxide films 3c and 3d having the film thickness shown in FIG. 5 are formed.
The cleaning conditions after plating are the same in FIG. 4 and FIG.
The difference in the oxide film thickness under the conditions is shown in FIGS.
Because the thickness of the plating film used in the experiment differs between
is there. If the plating thickness is different, the structure of the plating film and impurities
Oxidation is formed on the
This is because the films are different even under the same cleaning conditions. By the way
In addition, the plating film depends on the plating bath temperature and current density during plating.
Addition of plating conditions, differences in plating bath composition, brightener, etc.
It also depends on the type and amount of the agent.
【００３９】実施例７．上記実施例では洗浄水として６
０℃の脱イオン水を用いたが、水温は６０℃に限定され
ず、洗浄時間も３０秒と１２０秒とに限定されない。要
するに酸化膜の厚みが５ｎｍ以上異なるように設定すれ
ばよい。Embodiment 7 FIG. In the above embodiment, the cleaning water is 6
Although deionized water at 0 ° C. was used, the water temperature is not limited to 60 ° C., and the cleaning time is not limited to 30 seconds or 120 seconds. In short, the thickness of the oxide film may be set to be different by 5 nm or more.
【００４０】また、洗浄水の水温も同一温度に設定する
必要もない。すなわち、図４に示すように酸化膜の膜厚
が洗浄水温度によって制御できることを利用し、半田付
け部位２ａを４０℃以下の温度の洗浄水で洗浄させ、非
半田付け部位２ｂを５０℃以上の温度の洗浄水で洗浄さ
せることもできる。この成膜方法は第３の発明に係る表
面処理方法を構成している。このようにすると、半田付
け部位２ａと非半田付け部位２ｂとで酸化膜の膜厚が変
わる以外に、結晶構造を変えることができるから、より
一層半田ぬれ性を制御し易くなる。Further, it is not necessary to set the temperature of the washing water to the same temperature. That is, as shown in FIG. 4, utilizing the fact that the thickness of the oxide film can be controlled by the temperature of the cleaning water, the soldering portion 2a is cleaned with cleaning water having a temperature of 40 ° C. or less, and the non-soldering portion 2b is heated at 50 ° C. or more. Washing with washing water at a temperature of This film forming method constitutes the surface treatment method according to the third invention. By doing so, the crystal structure can be changed in addition to the change in the thickness of the oxide film between the soldered portion 2a and the non-soldered portion 2b, so that the solder wettability can be more easily controlled.
【００４１】実施例８．上述した実施例では、酸化膜の
結晶構造や膜厚を変えるに当たって洗浄水の温度を変え
る手法を採っていたが、図８に示すように、４０℃以下
の洗浄水中に半田付け部材を浸漬させ、この半田付け部
材の非半田付け部位にレーザ光を照射するようにしても
よい。Embodiment 8 FIG. In the above-described embodiment, the method of changing the temperature of the cleaning water to change the crystal structure and the film thickness of the oxide film is adopted. However, as shown in FIG. 8, the soldering member is immersed in the cleaning water of 40 ° C. or less. Alternatively, a laser beam may be applied to a non-soldering portion of the soldering member.
【００４２】図８は第４の発明に係る半田付け部材の表
面処理方法を説明するための図である。同図において、
１４はエネルギービームとしてのレーザ光で、このレー
ザ光は１００Ｗ／ｃｍ 2 のパワー密度のＡｒレーザであ
る。そして、４０℃の洗浄水中に半田付け部材Ｗを深さ
Ｄの位置に水平に配置し、この半田付け部材Ｗの非半田
付け部位２ｂに前記レーザ光１４を１０ｃｍ／ｍｉｎの
速度をもって走査させて照射した。なお、前記レーザ光
１４が透過する水の層の厚さ（深さＤ）としては、本実
施例では１ｍｍとした。FIG. 8 is a view for explaining a surface treatment method for a soldering member according to the fourth invention. In the figure,
Reference numeral 14 denotes a laser beam as an energy beam, and the laser beam has a power of 100 W / cm 2. An Ar laser having a power density of Then, the soldering member W is horizontally arranged at the position of the depth D in the washing water at 40 ° C., and the laser beam 14 is scanned at a speed of 10 cm / min on the non-soldering portion 2 b of the soldering member W. Irradiated. The thickness (depth D) of the water layer through which the laser light 14 passes was set to 1 mm in this embodiment.
【００４３】このように半田付け部材Ｗを水洗しながら
非半田付け部位２ｂにレーザ光１４を照射させると、レ
ーザ光１４が照射された部分は他の部分より高温になる
関係から、レーザ光照射部分での酸化膜厚を非照射部分
より厚くすることができ、あるいは、レーザ照射部分で
の酸化膜の構造を結晶質にできかつ非照射部分での酸化
膜の構造をアモルファスにできる。すなわち、半田ぬれ
性の制御を局所的に行うことができ、微小部品であって
も半田ぬれ性を容易に制御することができる。When the non-soldered portion 2b is irradiated with the laser beam 14 while washing the soldering member W with water as described above, the portion irradiated with the laser beam 14 becomes hotter than the other portions. The oxide film thickness at the portion can be made thicker than the non-irradiated portion, or the oxide film structure at the laser-irradiated portion can be made crystalline and the oxide film structure at the non-irradiated portion can be made amorphous. That is, the solder wettability can be locally controlled, and the solder wettability can be easily controlled even for a small component.
【００４４】（３）第５の発明に係る半田付け部材の表
面処理方法について 実施例９．第５の発明に係る半田付け部材の表面処理方
法を図９〜図１３によって詳細に説明する。図９は第５
の発明に係る表面処理方法によって酸化膜が成膜された
半田付け部材の要部を拡大して示す断面図、図１０はエ
チルアルコール混合率の異なる洗浄液の温度と半田ぬれ
性との関係を示すグラフ、図１１は２０℃のエタノー
ル，脱イオン水との混合液で洗浄したＮｉめっき表面の
ＥＳＣＡの結果を示す図、図１２は８０℃の脱イオン水
で３００秒間洗浄したＮｉめっき表面のＥＳＣＡの結果
を示す図である。図１３は第５の発明に係る半田付け部
材の表面処理方法を説明するための図で、同図（ａ）は
半田付け部位を洗浄している状態を示し、同図（ｂ）は
非半田付け部位を洗浄している状態を示す。これらの図
において前記図１ないし図３で説明したものと同一もし
くは同等部材については、同一符号を付し詳細な説明は
省略する。(3) Method for Surface Treatment of Solder Member According to Fifth Embodiment The surface treatment method for a soldering member according to the fifth invention will be described in detail with reference to FIGS. FIG. 9 shows the fifth
FIG. 10 is an enlarged sectional view showing a main part of a soldering member on which an oxide film is formed by the surface treatment method according to the invention, and FIG. 10 shows the relationship between the temperature of the cleaning liquid having different ethyl alcohol mixing ratio and the solder wettability. FIG. 11 is a graph showing the results of ESCA of the Ni plating surface washed with a mixed solution of ethanol and deionized water at 20 ° C., and FIG. 12 is a diagram showing the ESCA of the Ni plating surface washed with deionized water at 80 ° C. for 300 seconds. It is a figure which shows the result of. FIGS. 13A and 13B are views for explaining a surface treatment method for a soldering member according to the fifth invention. FIG. 13A shows a state where a soldering portion is being cleaned, and FIG. This shows a state in which the attachment site is being cleaned. In these drawings, the same or equivalent members as those described in FIGS. 1 to 3 are denoted by the same reference numerals, and detailed description is omitted.
【００４５】図１０は金属析出後の洗浄工程において洗
浄水中にエチルアルコールを混合した場合の洗浄温度と
半田ぬれ性の関係を示すグラフである。なお、メニスコ
グラフ法でのゼロクロスタイムを半田ぬれ性の指標とし
た。このメニスコグラフ法とは、ＩＳＯにおいては表面
張力法、ぬれバランス法（Wetting balance method）の
ことをいう。本法は、任意の形状の半田ぬれ性を比較す
るのに最も広く使われる試験法である。この試験法にお
けるゼロクロスタイムとは、試験片を溶融半田に浸漬後
から、試験片に半田がぬれる過程で表面張力に由来する
垂直成分の作用力が零になるところまでぬれた状態まで
の時間である。 FIG. 10 is a graph showing the relationship between the cleaning temperature and the solder wettability when ethyl alcohol is mixed in the cleaning water in the cleaning step after metal deposition. The zero cross time in the meniscograph method was used as an index of solder wettability. This meniscograph method is a surface in ISO
Tension method, wetting balance method
That means. This method compares the solder wettability of arbitrary shapes.
This is the most widely used test method. This test method
Zero crossing time is the time after the test piece is immersed in the molten solder.
From the surface tension in the process of solder wetting on the test piece
Until the force of the vertical component becomes zero
It's time.
【００４６】発明者らは、エチルアルコールを混合した
水で洗浄を行うと、Ｎｉめっき表面に生成される酸化膜
の組成が変化し、エチルアルコールの混合率が多くなる
にしたがって半田ぬれ性が高くなることを発見した。そ
こで、エチルアルコールが混合された洗浄液で半田付け
部位を洗浄することによって、この半田付け部位の酸化
膜の組成を非半田付け部位に対して変え、半田ぬれ性を
制御するようにした。When the inventors performed cleaning with water mixed with ethyl alcohol, the composition of the oxide film formed on the Ni plating surface changed, and the higher the mixing ratio of ethyl alcohol, the higher the solder wettability. I discovered that it would be. Therefore, by cleaning the soldering portion with a cleaning liquid mixed with ethyl alcohol, the composition of the oxide film at this soldering portion is changed with respect to the non-soldering portion to control the solder wettability.
【００４７】図９に示す酸化膜３は、半田付け部位２ａ
になる部分と非半田付け部位２ｂになる部分とでは膜厚
は略同じであるが、組成が異なっている。すなわち、半
田付け部位２ａ側には半田ぬれ性が高くなる組成の酸化
膜３ｘが形成され、非半田付け部位２ｂ側には半田ぬれ
性が低くなる組成の酸化膜３ｙが形成されている。この
ように構成することによって、半田ぬれ性を制御するこ
とができる。このため、レジスト等を用いることなく半
田付け箇所を限定でき、半田付け接合部の形状が安定
し、半田付け部の信頼性が向上する。The oxide film 3 shown in FIG.
And the part to be the non-soldering part 2b have substantially the same film thickness but different compositions. That is, the soldering portion 2a side is formed oxide film 3x compositions solder wettability is high, oxidation film 3y of the non-soldering portion 2b side solder wettability decreases composition is formed. With this configuration, it is possible to control the solder wettability. For this reason, the soldering portion can be limited without using a resist or the like, the shape of the soldering joint is stabilized, and the reliability of the soldering portion is improved.
【００４８】実施例１０．上述したように酸化膜３の組
成を部分的に変えるに当たっては、図１３に示すように
して行う。図１３において１５は脱イオン水に５０Ｖｏ
ｌ％のエチルアルコールを混合させた２０℃の洗浄液、
１６は８０℃の脱イオン水からなる洗浄水である。酸化
膜３の成膜は、半田付け部材Ｗにおける半田付け部位２
ａを前記洗浄液１５に３００秒間没入させて洗浄させ、
非半田付け部位２ｂを前記洗浄水１６に３０秒間没入さ
せて洗浄させることによって行う。なお、この成膜方法
が第５の発明に係る半田付け部材の表面処理方法を構成
している。Embodiment 10 FIG. As described above, the composition of the oxide film 3 is partially changed as shown in FIG. In FIG. 13, reference numeral 15 denotes 50 Vo in deionized water.
20 ° C. washing solution mixed with 1% ethyl alcohol,
Reference numeral 16 denotes washing water composed of deionized water at 80 ° C. The oxide film 3 is formed at the soldering portion 2 in the soldering member W.
a is immersed in the cleaning solution 15 for 300 seconds for cleaning,
This is performed by immersing the non-soldering portion 2b in the cleaning water 16 for 30 seconds to perform cleaning. This film forming method constitutes the surface treatment method of the soldering member according to the fifth invention.
【００４９】ここで、前記酸化膜３ｘと酸化膜３ｙとの
組成の違いを図１１および図１２によって説明する。図
１１は、脱イオン水にエチルアルコールを５０Ｖｏｌ％
混合した２０℃の洗浄液で３００秒間洗浄することによ
ってＮｉめっき表面に成膜された酸化膜３ｘのＥＳＣＡ
（Ｘ線光電子分光法のことで、ＸＰＳともいう）結果を
示す。同図（ａ）に示すＮｉ2p3/2 スペクトルにおい
て、Ｎｉのピーク強度ｅとＮｉの酸化物のピーク強度
ｅ′の比ｅ′／ｅをＥとし、同図（ｂ）に示すＯ1Sにお
いてＯのピーク強度をｅO とする。Here, the difference in composition between the oxide film 3x and the oxide film 3y will be described with reference to FIGS. FIG. 11 shows 50 vol% of ethyl alcohol in deionized water.
ESCA of oxide film 3x formed on Ni plating surface by washing with mixed cleaning solution at 20 ° C. for 300 seconds
The results (X-ray photoelectron spectroscopy, also referred to as XPS) are shown. In the Ni 2p3 / 2 spectrum shown in FIG. 7A, the ratio e ′ / e of the peak intensity e of Ni and the peak intensity e ′ of the oxide of Ni is represented by E, and O 1 S shown in FIG. Is assumed to be e O.
【００５０】図１２は、８０℃の脱イオン水で３０秒間
洗浄することによってＮｉめっき表面に成膜された酸化
膜３ｙのＥＳＣＡ結果を示す。同図（ａ）に示すＮｉ
2p3/2スペクトルにおいて、Ｎｉのピーク強度ｔとＮｉ
の酸化物のピーク強度ｔ′との比ｔ′／ｔをＴとし、同
図（ｂ）に示すＯ1SにおいてＯのピーク強度をｔO とす
る。FIG. 12 shows the ESCA results of the oxide film 3y formed on the Ni plating surface by washing with deionized water at 80 ° C. for 30 seconds. Ni shown in FIG.
In the 2p3 / 2 spectrum, Ni peak intensity t and Ni
The / t 'ratio t of the' peak intensity t of oxides is T, the peak intensity of O and t O in O 1S shown in FIG. (B).
【００５１】その場合、酸化膜３ｘと酸化膜３ｙの膜厚
が略同一（膜厚の違いが５ｎｍ以内）のときに、（Ｔ／
ｔO）−（Ｅ／ｅO）＝０．５４−０．４＝０．１４とし
た。この数式は、酸化膜の組成に関するもので、エタノ
ール含有水で洗浄することで組成が変化することを意味
している。この値が大きければ大きいほど酸化膜の組成
の違いが大きいことを意味し、相対的な半田ぬれ性の差
を十分確保できて半田付け部材のぬれの制御が容易にな
る。このように半田付け部材Ｗの表面に組成の異なる酸
化膜３ｘ，３ｙを形成したことにより、半田のぬれ性を
制御でき、レジスト等を用いることなく半田付け箇所を
限定でき、半田接合部形状が安定し、半田付け部の信頼
性が向上する。In this case, when the thicknesses of the oxide films 3x and 3y are substantially the same (the difference in thickness is within 5 nm), (T /
t O) - (it was the E / e O) = 0.54-0.4 = 0.14. This equation relates to the composition of the oxide film,
The composition changes by washing with water containing water
doing. The larger the value, the more the composition of the oxide film
Means a large difference in the relative solder wettability
Sufficient to control soldering of the soldering members.
You. By forming the oxide films 3x and 3y having different compositions on the surface of the soldering member W in this manner, the wettability of the solder can be controlled, the soldering location can be limited without using a resist or the like, and the shape of the solder joint portion can be reduced. Stable, and the reliability of the soldered portion is improved.
【００５２】実施例１１．上記実施例では、組成の異な
る酸化膜どうしの膜厚が略等しい（膜厚の違いが５ｎｍ
以内）ときに、（Ｔ／ｔO）−（Ｅ／ｅO）＝０．１４と
したが、（Ｔ／ｔO）−（Ｅ／ｅO）の値が０．０５より
大きければ、充分に半田ぬれ性が異なるようになって半
田付け箇所を限定することができる。Embodiment 11 FIG. In the above embodiment, the thicknesses of the oxide films having different compositions are substantially equal (the difference in thickness is 5 nm).
(Within), (T / t O ) − (E / e O ) = 0.14, but if the value of (T / t O ) − (E / e O ) is larger than 0.05, it is sufficient. Therefore, the solder wettability is different, so that the soldering location can be limited.
【００５３】実施例１２． 上述した各実施例では、半田ぬれ性が高くなる組成の酸
化膜３ｘと、半田ぬれ性が低くなる組成の酸化膜３ｙと
の膜厚差を５ｎｍ以内としたが、半田ぬれ性が低くなる
組成の酸化膜３ｙの膜厚を他方の酸化膜３ｘより５ｎｍ
以上厚くすると、ぬれ性の違いがより一層顕著になる。Embodiment 12 FIG. In each of the above-described embodiments, the difference in thickness between the oxide film 3x having a composition having a high solder wettability and the oxide film 3y having a composition having a low solder wettability is within 5 nm. Oxide film 3y is 5 nm thicker than the other oxide film 3x.
When the thickness is thicker, the difference in wettability becomes more remarkable.
【００５４】また、組成の違いとしてはＮｉＯ、Ｎｉ2
Ｏ3の違いでもよく、それらの酸化膜中にＮｉ（ＯＨ）2
やＨが混入することで組成の違いを構成してもよい。The difference in composition is NiO, Ni 2
O 3 may be different, and Ni (OH) 2
A difference in composition may be formed by mixing H or H.
【００５５】実施例１３． さらに、上述した各実施例では、半田付け部位２ａを洗
浄するときにエチルアルコールを５０Ｖｏｌ％含んだ２
０℃の脱イオン水を用いたが、エチルアルコールの含有
量や水温はこれに限定されるものではない。さらにま
た、脱イオン水に混合するアルコールはエチルアルコー
ルに限定されることはなく、メチルアルコールでもよ
く、さらには多価アルコールでもよい。Embodiment 13 FIG. Further, in each of the above-described embodiments, when cleaning the soldering portion 2a, the soldering portion 2a containing 50 Vol% of ethyl alcohol was used.
Although deionized water at 0 ° C. was used, the content of ethyl alcohol and the water temperature are not limited thereto. Furthermore, the alcohol mixed with the deionized water is not limited to ethyl alcohol, but may be methyl alcohol, or may be polyhydric alcohol.
【００５６】加えて、非半田付け部位を洗浄するに当た
って８０℃の脱イオン水を用いたが、その温度は適宜変
更できるということはいうまでもない。In addition, although deionized water of 80 ° C. was used for cleaning the non-soldering portion, it is needless to say that the temperature can be appropriately changed.
【００５７】実施例１４．なお、上述した実施例では、
Ｎｉめっきを、光沢剤を添加したワット浴によって行っ
たが、ワット浴に限ることなくスルファミン酸浴等でも
よい。しかも、薬品含量も適宜変更できる。また、Ｎｉ
めっき皮膜２として、光沢剤を添加しためっき液から形
成した光沢Ｎｉめっきを用いたが、光沢剤を添加しない
めっき浴から形成した無光沢Ｎｉめっき皮膜を用いても
よい。さらに、上述した各実施例で使用した半田付け部
材は、電気めっきから得られたＮｉめっき部品である
が、Ｎｉめっき皮膜はＮｉ基合金でもよい。なお、電気
めっきに限定されることもなく、無電解Ｎｉめっきによ
って得られたＮｉ−Ｐ、Ｎｉ−Ｂ等でもよい。Embodiment 14 FIG. In the embodiment described above,
Although the Ni plating was performed using a Watt bath to which a brightener was added, the present invention is not limited to the Watt bath, and a sulfamic acid bath or the like may be used. In addition, the drug content can be appropriately changed. Also, Ni
As the plating film 2, bright Ni plating formed from a plating solution to which a brightener is added is used, but a dull Ni plating film formed from a plating bath to which no brightener is added may be used. Furthermore, although the soldering member used in each of the above-described embodiments is a Ni-plated component obtained by electroplating, the Ni-plated film may be a Ni-based alloy. In addition, it is not limited to electroplating, and may be Ni-P, Ni-B, or the like obtained by electroless Ni plating.
【００５８】[0058]
【発明の効果】以上説明したように本発明によれば、Ｎ
ｉめっき部品からなる半田付け部材の表面の酸化膜に半
田ぬれ性の高い部分と半田ぬれ性の低い部分とを設けた
ため、半田接合部（フィレット）の形状が安定するか
ら、半田付け部の信頼性を向上させることができる。As described above, according to the present invention, N
Since the high solder wettability portion and the low solder wettability portion are provided on the oxide film on the surface of the soldering member made of the i-plated component, the shape of the solder joint (fillet) is stabilized, so the reliability of the soldering portion is improved. Performance can be improved.
【００５９】また、金属析出後の洗浄工程にて前記酸化
膜が成膜されるため、酸化膜を成膜させるための特別な
装置を必要としない。このため、従来の半田付け部材製
造装置を用いて酸化膜を成膜できるから、コストを可及
的低く抑えることができ、半田付け部材を安価に得るこ
とができる。Further, since the oxide film is formed in the cleaning step after the metal deposition, a special device for forming the oxide film is not required. For this reason, since the oxide film can be formed using the conventional soldering member manufacturing apparatus, the cost can be suppressed as low as possible, and the soldering member can be obtained at low cost.
【図１】洗浄水温度とＮｉめっき表面の酸化膜の結晶構
造との関係を示すＲＨＥＥＤ分析結果の模式図である。FIG. 1 is a schematic diagram of RHEED analysis results showing a relationship between a cleaning water temperature and a crystal structure of an oxide film on a Ni plating surface.
【図２】第１の発明に係る半田付け部材の要部を拡大し
て示す断面図である。FIG. 2 is an enlarged sectional view showing a main part of the soldering member according to the first invention.
【図３】第１の発明に係る半田付け部材を形成するため
の製造方法を示す図で、同図（ａ）は半田付け部位を洗
浄している状態を示し、同図（ｂ）は非半田付け部位を
洗浄している状態を示す。3A and 3B are views showing a manufacturing method for forming a soldering member according to the first invention, wherein FIG. 3A shows a state in which a soldering portion is being cleaned, and FIG. This shows a state where the soldering part is being cleaned.
【図４】洗浄水に半田付け部材を３０秒間浸漬させた場
合の洗浄水温度と酸化膜の膜厚との関係を示すグラフで
ある。FIG. 4 is a graph showing a relationship between cleaning water temperature and oxide film thickness when a soldering member is immersed in cleaning water for 30 seconds.
【図５】第２の発明に係る半田付け部材の要部を拡大し
て示す断面図である。FIG. 5 is an enlarged sectional view showing a main part of a soldering member according to a second invention.
【図６】洗浄水として６０℃の脱イオン水を使用したと
きの洗浄時間と酸化膜の膜厚との関係を示すグラフであ
る。FIG. 6 is a graph showing a relationship between a cleaning time and a thickness of an oxide film when deionized water at 60 ° C. is used as cleaning water.
【図７】第２の発明に係る半田付け部材を形成するため
の製造方法を示す図で、同図（ａ）は半田付け部位を洗
浄している状態を示し、同図（ｂ）は非半田付け部位を
洗浄している状態を示す。FIGS. 7A and 7B are diagrams showing a manufacturing method for forming a soldering member according to the second invention, wherein FIG. 7A shows a state in which a soldering portion is cleaned, and FIG. This shows a state where the soldering part is being cleaned.
【図８】第４の発明に係る半田付け部材の表面処理方法
を説明するための図である。FIG. 8 is a view for explaining a surface treatment method for a soldering member according to a fourth invention.
【図９】第５の発明に係る表面処理方法によって酸化膜
が成膜された半田付け部材の要部を拡大して示す断面図
である。FIG. 9 is an enlarged sectional view showing a main part of a soldering member on which an oxide film is formed by a surface treatment method according to a fifth invention.
【図１０】エチルアルコール混合率の異なる洗浄液の温
度と半田ぬれ性との関係を示すグラフである。FIG. 10 is a graph showing the relationship between the temperature of cleaning solutions having different ethyl alcohol mixing ratios and the solder wettability.
【図１１】２０℃のエタノール，脱イオン水との混合液
で洗浄したＮｉめっき表面のＥＳＣＡの結果を示す図で
ある。FIG. 11 is a diagram showing the results of ESCA of a Ni plating surface washed with a mixed solution of ethanol and deionized water at 20 ° C.
【図１２】８０℃の脱イオン水で３０秒間洗浄したＮｉ
めっき表面のＥＳＣＡの結果を示す図である。FIG. 12 shows Ni washed for 30 seconds with deionized water at 80 ° C.
It is a figure showing the result of ESCA of a plating surface.
【図１３】第５の発明に係る半田付け部材の表面処理方
法を説明するための図で、同図（ａ）は半田付け部位を
洗浄している状態を示し、同図（ｂ）は非半田付け部位
を洗浄している状態を示す。13A and 13B are views for explaining a surface treatment method of a soldering member according to a fifth invention, wherein FIG. 13A shows a state where a soldering portion is being cleaned, and FIG. This shows a state where the soldering part is being cleaned.
【図１４】従来のＮｉめっき式半田付け部材を部分的に
拡大して示す断面図である。FIG. 14 is a partially enlarged cross-sectional view showing a conventional Ni-plated soldering member.
【図１５】従来から一般的に行われているＮｉめっき方
法の一例を示す工程図である。FIG. 15 is a process chart showing an example of a Ni plating method generally performed conventionally.
【図１６】図１６はＮｉめっき法におけるめっき材の洗
浄方法を示す構成図である。FIG. 16 is a configuration diagram showing a method of cleaning a plating material in a Ni plating method.
【図１７】従来の半田付け部材を半田付けしたときの半
田付け部を拡大して示す断面図で、同図（ａ）は半田付
け不良の状態を示し、同図（ｂ）は半田付け良好の状態
を示す。FIG. 17 is an enlarged cross-sectional view showing a soldering portion when a conventional soldering member is soldered. FIG. 17A shows a state of poor soldering, and FIG. 17B shows good soldering. The state of is shown.
１ 基材 ２ Ｎｉめっき皮膜 ３ 酸化膜 ３ａ アモルファス酸化膜 ３ｂ 結晶質酸化膜 １１ 洗浄水（５℃） １２ 洗浄水（９０℃） １３ 脱イオン水（６０℃） １４ レーザ光 １５ 洗浄液（エチルアルコール含有，２０℃） １６ 洗浄水（８０℃） Ｗ 半田付け部材Reference Signs List 1 base material 2 Ni plating film 3 oxide film 3a amorphous oxide film 3b crystalline oxide film 11 cleaning water (5 ° C) 12 cleaning water (90 ° C) 13 deionized water (60 ° C) 14 laser light 15 cleaning liquid (containing ethyl alcohol ) , 20 ° C) 16 cleaning water (80 ° C) W Soldering member
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−56972（ＪＰ，Ａ) 特開 平１−309780（ＪＰ，Ａ) 表面技術 44巻 11号（1993）中岡他 124〜128頁 ＮＡＫＡＯＫＡ ＥＴ ＡＬ．”ＳＵ ＲＦＡＣＥ ＯＸＩＤＡＴＩＯＮ ＯＦ ＮＩＣＫＥＬ ＰＬＡＴＩＮＧ ＩＮ ＴＨＥ ＲＩＮＳＩＮＧ ＰＲＯＣＥ ＳＳ”，ＭＥＴＡＬ ＦＩＮＩＳＨＩＮ Ｇ，91（５）：７−10；1993 (58)調査した分野(Int.Cl.6，ＤＢ名) B23K 1/20 B23K 1/00 C23C 18/31 C25D 5/48──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-59-56972 (JP, A) JP-A-1-309780 (JP, A) Surface technology 44 No. 11 (1993) Nakaoka et al. ET AL. "SU RFACE OXIDATION OF NICKEL PLATING IN THE RINGSING PROCESS SS", METAL FINISHING G, 91 (5): 7-10; 1993 (58) Fields investigated (Int. Cl. 6 , DB name) B23K 1/20 B23K 1 / 00 C23C 18/31 C25D 5/48
Claims (5)
け部材の表面構造において、ニッケルめっき部分の表面
に生成される酸化膜を、半田付け部位では非晶質とし、
非半田付け部位では結晶質としたことを特徴とする半田
付け部材の表面構造。In a surface structure of a soldering member having a surface plated with nickel, an oxide film formed on a surface of a nickel-plated portion is made amorphous at a soldering portion;
The surface structure of the soldering member, wherein the non-soldering part is made crystalline.
け部材の表面構造において、ニッケルめっき部分の表面
に生成される酸化膜を、半田付け部位では膜厚を比較的
薄く形成し、非半田付け部位では前記半田付け部位より
膜厚を厚く形成したことを特徴とする半田付け部材の表
面構造。2. In a surface structure of a soldering member whose surface is nickel-plated, an oxide film formed on a surface of a nickel-plated portion is formed to have a relatively thin film thickness at a soldering portion, and a non-soldering film is formed. The surface structure of the soldering member, wherein the portion has a greater thickness than the soldering portion.
を、ニッケルめっき後に半田付け部材を洗浄するとき
に、半田付け部位を略４０℃以下の温度の洗浄液によっ
て洗浄し、非半田付け部位を前記温度より十分に高い温
度の洗浄液によって洗浄して成膜させることを特徴とす
る半田付け部材の表面処理方法。3. When the oxide film according to claim 1 or 2 is cleaned with a cleaning solution having a temperature of about 40 ° C. or less when the soldering member is cleaned after nickel plating, the non-soldering portion is cleaned. Cleaning with a cleaning liquid at a temperature sufficiently higher than the above temperature to form a film.
施した後、この半田付け部材を略４０℃以下の温度の洗
浄液に浸漬させ、この状態で非半田付け部位にエネルギ
ービームを照射して非半田付け部位を前記温度より十分
に高い温度に高めることを特徴とする半田付け部材の表
面処理方法。4. After applying nickel plating to the surface of the soldering member, the soldering member is immersed in a cleaning solution having a temperature of about 40 ° C. or less, and in this state, the non-soldering portion is irradiated with an energy beam and irradiated with an energy beam. A surface treatment method for a soldering member, wherein the temperature of a soldering portion is raised to a temperature sufficiently higher than the above temperature.
施した後、この半田付け部材を洗浄するときに、半田付
け部位を略４０℃以下の温度のアルコール系洗浄液によ
って洗浄して半田付け部位に半田ぬれ性が高い組成の酸
化膜を成膜させ、非半田付け部位を前記温度より十分に
高い温度の洗浄液によって洗浄して非半田付け部位に前
記酸化膜より半田ぬれ性が低い組成の酸化膜を成膜させ
ることを特徴とする半田付け部材の表面処理方法。5. After the surface of the soldering member is plated with nickel, when the soldering member is cleaned, the soldered portion is cleaned with an alcohol-based cleaning liquid at a temperature of about 40 ° C. or less, and the soldered portion is cleaned. An oxide film having a composition having a high solder wettability is formed, and the non-soldering portion is washed with a cleaning liquid at a temperature sufficiently higher than the above temperature, and an oxide film having a composition having a lower solder wettability than the oxide film is applied to the non-soldering portion. A method for surface treatment of a soldering member, characterized by forming a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3530893A JP2809030B2 (en) | 1993-02-24 | 1993-02-24 | Surface structure of soldering member and surface treatment method of soldering member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3530893A JP2809030B2 (en) | 1993-02-24 | 1993-02-24 | Surface structure of soldering member and surface treatment method of soldering member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06246435A JPH06246435A (en) | 1994-09-06 |
| JP2809030B2 true JP2809030B2 (en) | 1998-10-08 |
Family
ID=12438168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3530893A Expired - Fee Related JP2809030B2 (en) | 1993-02-24 | 1993-02-24 | Surface structure of soldering member and surface treatment method of soldering member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2809030B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7230867B2 (en) * | 2020-03-02 | 2023-03-01 | 株式会社村田製作所 | Manufacturing method of ceramic electronic component |
-
1993
- 1993-02-24 JP JP3530893A patent/JP2809030B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| ＮＡＫＡＯＫＡ ＥＴ ＡＬ．"ＳＵＲＦＡＣＥ ＯＸＩＤＡＴＩＯＮ ＯＦ ＮＩＣＫＥＬ ＰＬＡＴＩＮＧ ＩＮ ＴＨＥ ＲＩＮＳＩＮＧ ＰＲＯＣＥＳＳ"，ＭＥＴＡＬ ＦＩＮＩＳＨＩＮＧ，９１（５）：７−１０；１９９３ |
| 表面技術 ４４巻 １１号（１９９３）中岡他 １２４〜１２８頁 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06246435A (en) | 1994-09-06 |
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