JP2002105679A - Solution for removing metallic oxide film and removing method using the same - Google Patents
Solution for removing metallic oxide film and removing method using the sameInfo
- Publication number
- JP2002105679A JP2002105679A JP2000293449A JP2000293449A JP2002105679A JP 2002105679 A JP2002105679 A JP 2002105679A JP 2000293449 A JP2000293449 A JP 2000293449A JP 2000293449 A JP2000293449 A JP 2000293449A JP 2002105679 A JP2002105679 A JP 2002105679A
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- metal oxide
- metal
- solution
- removal
- 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.)
- Granted
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 238000005237 degreasing agent Methods 0.000 claims abstract description 7
- 239000013527 degreasing agent Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000000176 sodium gluconate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 11
- 238000007788 roughening Methods 0.000 abstract description 4
- 238000007747 plating Methods 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 17
- 229910000679 solder Inorganic materials 0.000 description 14
- 238000007654 immersion Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属表面に形成さ
れる金属酸化物の被膜を除去する技術に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for removing a metal oxide film formed on a metal surface.
【０００２】[0002]
【従来の技術】従来より、金属表面に形成される金属酸
化物の被膜は、エッチング法や電解還元法を用いて除去
する方法が知られている。2. Description of the Related Art Conventionally, there has been known a method of removing a metal oxide film formed on a metal surface by using an etching method or an electrolytic reduction method.
【０００３】エッチング法の場合、例えば、Ｃｕの表面
に形成されたＣｕの酸化物被膜を除去するには、硫酸系
溶液などの酸性エッチング液に浸漬することにより、Ｃ
ｕを腐食し、表面に形成されたＣｕの酸化物被膜を除去
する方法がとられる。In the case of the etching method, for example, in order to remove a Cu oxide film formed on the surface of Cu, the Cu film is immersed in an acidic etching solution such as a sulfuric acid solution.
Then, a method is employed in which u is corroded and an oxide film of Cu formed on the surface is removed.
【０００４】このエッチング法による場合、Ｃｕ自体を
腐食させることにより、表面に形成されたＣｕの酸化物
被膜を除去するので、その酸化物被膜の厚みよりも深い
位置までエッチングしなければ、表面に形成された酸化
物被膜を全て除去することができない。即ち、エッチン
グ法ではオーバーエッチング状態にするため、金属酸化
物被膜の除去された金属表面は荒れた状態になり易い。In this etching method, the Cu oxide film formed on the surface is removed by corroding the Cu itself. Therefore, if the etching is not performed to a position deeper than the thickness of the oxide film, the surface may be etched. All the formed oxide films cannot be removed. That is, since the etching method is over-etched, the metal surface from which the metal oxide film has been removed tends to be rough.
【０００５】このような荒れた金属表面は、後工程でめ
っき処理を行う場合、その表面に形成されるめっき性状
に大きく影響し、特に、微細な部分にめっき処理を行う
微細配線めっきでは、平滑且つ均一なめっき処理ができ
ないことになる。また、エッチング法によると、スマッ
トが生成して後工程に不具合を生じたり、水素脆性の問
題が生じることもある。[0005] Such a rough metal surface greatly affects the plating properties formed on the surface when a plating process is performed in a later step. In addition, uniform plating cannot be performed. In addition, according to the etching method, a smut is generated, which may cause a problem in a subsequent process or a problem of hydrogen embrittlement.
【０００６】一方、電解還元法の場合は、金属酸化物の
被膜を形成した金属を陰極となるように通電し、金属酸
化物を還元することでその被膜を除去するものである。
しかし、この電解還元法は、通電操作が可能なものに対
しては有効であるが、金属酸化物被膜を形成した金属へ
の通電操作が行えない状態の場合には採用することがで
きないものである。On the other hand, in the case of the electrolytic reduction method, a metal on which a metal oxide film is formed is energized so as to serve as a cathode, and the metal oxide is reduced to remove the film.
However, this electrolytic reduction method is effective for those that can be energized, but cannot be used when the energization operation cannot be performed on the metal on which the metal oxide film is formed. is there.
【０００７】[0007]
【発明が解決しようとする課題】そこで、本発明は、金
属表面に形成される金属酸化物被膜を、従来のエッチン
グ法による除去の場合にように、除去後の金属表面が荒
らされることなく、平滑且つ均一に除去処理が行え、通
電操作が行えない状態にある金属の表面に形成された金
属酸化物被膜も除去することができる技術を提供せんと
するものである。SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for removing a metal oxide film formed on a metal surface without roughening the metal surface after the removal as in the case of the conventional etching method. It is an object of the present invention to provide a technique capable of performing a smooth and uniform removal treatment and also removing a metal oxide film formed on a surface of a metal in a state where an energization operation cannot be performed.
【０００８】[0008]
【課題を解決するための手段】かかる課題を解決するた
め、本発明者らは、金属酸化物被膜自体を、通電処理を
行うことなく、金属酸化物を還元する方法について種々
の検討を行った。その結果、アルカリ脱脂剤に還元剤を
加えたものを用いると、エッチング法のように金属表面
を荒らすことなく、金属酸化物を還元してその被膜を除
去できることを見出したのである。Means for Solving the Problems In order to solve such problems, the present inventors have conducted various studies on a method for reducing a metal oxide without subjecting the metal oxide coating itself to an electric current treatment. . As a result, they have found that using an alkaline degreasing agent added with a reducing agent can reduce the metal oxide and remove the film without roughening the metal surface unlike the etching method.
【０００９】本発明に係る金属酸化物被膜の除去液は、
アルカリ脱脂剤と還元剤とを含有するものであり、この
除去液に金属酸化物被膜を表面に形成した金属を浸漬さ
せると、除去液中の還元剤による還元反応によって水素
が発生し、この水素が金属酸化物を還元することで、金
属酸化物被膜の除去が可能となるのである。The solution for removing a metal oxide film according to the present invention comprises:
It contains an alkaline degreasing agent and a reducing agent, and when a metal having a metal oxide film formed on its surface is immersed in the removing solution, hydrogen is generated by a reduction reaction by the reducing agent in the removing solution. Reduces the metal oxide, which makes it possible to remove the metal oxide film.
【００１０】本発明の金属酸化物被膜の除去液では、金
属酸化物被膜は還元反応により除去されるので、従来の
エッチング法のように、金属自体がオーバーエッチング
されることはなく、除去後の金属表面は平滑で、均一な
状態とすることが可能である。また、還元剤による還元
反応を利用するものであるため、電解還元法のように通
電操作を全く必要としないため、通電操作が困難な場合
においても、本発明の除去液を用いれば、金属酸化物被
膜の除去が可能となる。In the metal oxide film removing solution of the present invention, the metal oxide film is removed by a reduction reaction, so that the metal itself is not over-etched unlike the conventional etching method, and the metal after the removal is removed. The metal surface can be made smooth and uniform. In addition, since a reduction reaction using a reducing agent is used, no energization operation is required at all as in the electrolytic reduction method. Therefore, even when the energization operation is difficult, the removal solution of the present invention can be used to remove metal oxide. The object film can be removed.
【００１１】本発明の金属酸化物被膜の除去液における
アルカリ脱脂剤は、一般的に知られているものを用いる
ことができ、炭酸ナトリウム、水酸化ナトリウム、メタ
ケイ酸ナトリウム、リン酸塩、ケイ酸塩、グルコン酸塩
のいずれか１種又は２種以上を用いることが好ましいも
のである。As the alkaline degreasing agent in the metal oxide film removing solution of the present invention, generally known ones can be used, and sodium carbonate, sodium hydroxide, sodium metasilicate, phosphate, and silicic acid can be used. It is preferable to use one or more of a salt and a gluconate.
【００１２】また、本発明の金属酸化物被膜の除去液に
おける還元剤は、水素化ホウ素ナトリウム、水素化ホウ
素カリウム、ジメチルアミンボランのいずれか１種又は
２種以上を用いることが好ましい。これらの還元剤は、
上記したアルカリ脱脂剤と混合された状態において、安
定した還元反応を生じるからである。It is preferable to use one or more of sodium borohydride, potassium borohydride and dimethylamine borane as the reducing agent in the metal oxide film removing solution of the present invention. These reducing agents are
This is because a stable reduction reaction occurs in a state of being mixed with the above-described alkali degreasing agent.
【００１３】本発明の金属酸化物被膜の除去液によっ
て、その金属酸化物被膜を除去するには、表面に金属酸
化物の被膜が形成された金属を除去液中に浸漬させる方
法によればよい。これにより、金属酸化物被膜に、還元
反応による水素が発生し、その水素により金属酸化物が
還元がされることになるからである。このように、本発
明の金属酸化物被膜の除去方法では、通電操作を必要と
しないので、通電操作が困難なものに対して非常に有効
なものである。但し、本発明の除去方法では、通電操作
を同時的に使用して、金属酸化物被膜を除去することも
可能である。In order to remove the metal oxide film with the metal oxide film removing solution of the present invention, a method in which the metal having the metal oxide film formed on the surface may be immersed in the removing solution. . Thereby, hydrogen is generated in the metal oxide film by the reduction reaction, and the hydrogen reduces the metal oxide. As described above, the method for removing a metal oxide film according to the present invention does not require an energizing operation, and thus is very effective for those in which energizing operation is difficult. However, in the removal method of the present invention, it is also possible to remove the metal oxide film by simultaneously using the energizing operation.
【００１４】本発明の金属酸化被膜の除去方法では、ｐ
Ｈ１０〜１４、液温１０〜８０℃の条件で還元反応を進
行させるようにすることが好ましい。ｐＨ１０未満であ
ると、還元剤の加水分解反応が急速に起こり、いわゆる
泡立ち状態となった水素が発生し、金属酸化物の還元能
力が著しく低下し、金属酸化物被膜の除去効率が悪くな
るからである。また、ｐＨ１４を越えると、還元剤の加
水分解反応が低くなり、水素の発生が少なくなり、金属
酸化物被膜の除去効率が悪くなるからである。そして、
液温についてもｐＨの場合と同様で、１０℃未満である
と還元剤の加水分解反応が低くなり、８０℃を越えると
還元剤の加水分解反応が急速に起こり、泡立ち状態の水
素が発生することになり、この１０〜８０℃液温範囲を
超えると、金属酸化物被膜の除去効率が悪くなるためで
ある。In the method for removing a metal oxide film according to the present invention, p
It is preferable that the reduction reaction proceed under the conditions of H10 to H14 and a liquid temperature of 10 to 80C. When the pH is less than 10, the hydrolysis reaction of the reducing agent rapidly occurs, so-called bubbling hydrogen is generated, the reducing ability of the metal oxide is remarkably reduced, and the removal efficiency of the metal oxide film is deteriorated. It is. On the other hand, when the pH exceeds 14, the hydrolysis reaction of the reducing agent is reduced, the generation of hydrogen is reduced, and the removal efficiency of the metal oxide film is deteriorated. And
As for the liquid temperature, the same as in the case of pH, when the temperature is lower than 10 ° C., the hydrolysis reaction of the reducing agent decreases, and when the temperature exceeds 80 ° C., the hydrolysis reaction of the reducing agent rapidly occurs, and bubbling hydrogen is generated. If the temperature exceeds the liquid temperature range of 10 to 80 ° C., the removal efficiency of the metal oxide film deteriorates.
【００１５】[0015]
【発明の実施の形態】以下、本発明の実施形態について
説明する。この本実施形態では、下地導電層を表面に形
成した基板上へ、所定厚みのＮｉめっきをして回路を形
成し、それに絶縁膜を塗布した評価サンプルを使用した
場合を例にして説明する。Embodiments of the present invention will be described below. In this embodiment, an example will be described in which a circuit is formed by plating a predetermined thickness of Ni on a substrate having a base conductive layer formed on the surface, and an evaluation sample obtained by applying an insulating film to the circuit is used as an example.
【００１６】この評価サンプルは、まず、基材表面へ下
地導電層を形成したものに、レジストを塗布することで
パターンニングをし、電気めっき法にてＮｉめっき処理
して、下地導電層上に所定回路を形成した。この電気め
っきは、厚さ３μｍのＮｉめっき処理したものである。
基板表面の下地導電層上にＮｉめっきによる所定回路を
形成した後、レジスト及び下地導電層を除去して、形成
した回路の必要部分のみ露出したパターンを形成するよ
うに絶縁膜を被覆した。その後、このパターンニングし
た絶縁膜を硬化するために、約３５０℃で、１時間の熱
処理を行った。このようにして形成された評価サンプル
は、図１に示す断面形状のもので、基板１表面の下地導
電層２上へＮｉめっき３により回路が形成されており、
その周りには絶縁膜４が被覆された状態となっている。
そして、絶縁膜４が被覆されていない部分、即ち、露出
したＮｉめっき３表面には、絶縁膜４を硬化するために
行う熱処理により、Ｎｉ酸化物被膜５が形成された状態
となっている。This evaluation sample is firstly patterned by applying a resist to a base conductive layer formed on the surface of the base material, and then Ni plating by an electroplating method. A predetermined circuit was formed. This electroplating is a 3 μm-thick Ni plating process.
After forming a predetermined circuit by Ni plating on the underlying conductive layer on the substrate surface, the resist and the underlying conductive layer were removed, and the insulating film was coated so as to form a pattern exposing only necessary portions of the formed circuit. Thereafter, in order to cure the patterned insulating film, heat treatment was performed at about 350 ° C. for one hour. The evaluation sample thus formed has the cross-sectional shape shown in FIG. 1, and a circuit is formed by Ni plating 3 on the underlying conductive layer 2 on the surface of the substrate 1.
The surroundings are covered with an insulating film 4.
The portion not covered with the insulating film 4, that is, the exposed surface of the Ni plating 3 is in a state where the Ni oxide film 5 is formed by the heat treatment performed to cure the insulating film 4.
【００１７】この評価サンプルは、半導体等の電子部品
製造工程を想定して作成したものである。例えば、半導
体等の電子部品製造工程では、このＮｉめっきの上へ、
更に無電解置換Ａｕめっき行い、そこへ半田ボールを接
合して半田バンプを形成するのである。This evaluation sample was prepared assuming a process for manufacturing an electronic component such as a semiconductor. For example, in the process of manufacturing electronic components such as semiconductors, on this Ni plating,
Further, electroless Au plating is performed, and a solder ball is bonded thereto to form a solder bump.
【００１８】つまり、図１で示すＮｉめっき３表面に形
成されるＮｉ酸化物被膜５は、後のＡｕめっき処理の障
害になる。そのために、このＮｉ酸化物被膜５の除去処
理が必要となるのである。また、本実施形態における評
価サンプルでは、Ｎｉめっき処理後に被覆される絶縁膜
４が存在しており、下地導電層２も除去されているた
め、通電を行うことが困難な状態となっている。That is, the Ni oxide film 5 formed on the surface of the Ni plating 3 shown in FIG. 1 becomes an obstacle to the subsequent Au plating. Therefore, the Ni oxide film 5 needs to be removed. In addition, in the evaluation sample of the present embodiment, the insulating film 4 to be coated after the Ni plating treatment is present, and the underlying conductive layer 2 is also removed, so that it is difficult to conduct electricity.
【００１９】次に、本実施形態における金属酸化物被膜
の除去液Ａについて説明する。この除去液Ａの組成を表
１に示す。Next, the solution A for removing the metal oxide film in this embodiment will be described. Table 1 shows the composition of the removal liquid A.
【００２０】[0020]
【表１】 [Table 1]
【００２１】また、従来から用いられている硫酸−過酸
化水素系の除去液Ｂを、比較のために使用した。この除
去液Ｂの組成を表２に示す。A conventional sulfuric acid-hydrogen peroxide-based removing solution B was used for comparison. Table 2 shows the composition of the removal liquid B.
【００２２】[0022]
【表２】 [Table 2]
【００２３】本実施形態の除去液Ａにおける酸化物被膜
の除去能力は、先に説明したバンプ形成の製造工程にお
けるＮｉの酸化物被膜を除去することにより調べた。具
体的には、図１で示した評価サンプル、即ち、下地導電
層を形成した基材に、３μｍ厚Ｎｉめっきによる回路を
形成して、その後絶縁膜を塗布し、絶縁膜の硬化熱処理
を行ったものを準備した。そして、この評価サンプルを
上記した除去液Ａ及びＢのそれぞれに浸漬して、Ｎｉ酸
化物被膜の除去を行った。除去能力評価は、除去処理後
の評価サンプルにおけるＮｉめっき表面をオージェ電子
分光分析により、表面から深さ方向への酸素量濃度の分
析をすることで酸化物の除去状態を確認し、また、金属
顕微鏡によりその表面状態を観察することによって行っ
た。The ability of the removing solution A of the present embodiment to remove the oxide film was examined by removing the Ni oxide film in the above-described bump formation process. Specifically, a circuit is formed by 3 μm-thick Ni plating on the evaluation sample shown in FIG. 1, that is, the substrate on which the underlying conductive layer is formed, and then an insulating film is applied, and a heat treatment for curing the insulating film is performed. Was prepared. Then, this evaluation sample was immersed in each of the above-mentioned removing liquids A and B to remove the Ni oxide film. The removal ability was evaluated by analyzing the Ni-plated surface of the evaluation sample after the removal treatment by Auger electron spectroscopy and analyzing the concentration of oxygen in the depth direction from the surface to confirm the removal state of the oxide. This was performed by observing the surface condition with a microscope.
【００２４】除去液Ａでは、評価サンプルを浸漬する際
の時間を５、１０、１５分間の３通りに変えて行い、除
去液Ｂでは２分間の浸漬を行った。除去液Ａ及び除去液
ＢでＮｉの酸化物被膜を除去した評価サンプル表面のオ
ージェ分析結果を図２に示す。The removing liquid A was immersed in the evaluation sample for three times of 5, 10 and 15 minutes, and the removing liquid B was immersed for 2 minutes. FIG. 2 shows the Auger analysis results of the surface of the evaluation sample from which the Ni oxide film was removed with the removing solution A and the removing solution B.
【００２５】図２凡例中、Ａ５、Ａ１０、Ａ１５と示し
ているのが、除去液Ａで浸漬時間を５、１０、１５分間
と変えた場合の結果に対応している。横軸は、スパッタ
時間を示し、縦軸は検出された酸素原子濃度を示してい
る。このオージェ分析でのスパッタレートは、６０Å／
ｍｉｎであった。The legends A5, A10 and A15 in the legend in FIG. 2 correspond to the results when the immersion time was changed to 5, 10 and 15 minutes with the removing solution A. The horizontal axis indicates the sputtering time, and the vertical axis indicates the detected oxygen atom concentration. The sputter rate in this Auger analysis is 60 ° /
min.
【００２６】図２で示すように、従来の除去液Ｂによる
ものに比べ、除去液Ａの方が表面のＮｉ酸化物を除去し
ていることが確認された。特に、除去液Ａで、１０分及
び１５分間浸漬したものは、明らかにＮｉ酸化物被膜の
除去が進行していることが判明した。As shown in FIG. 2, it was confirmed that the removing solution A removed Ni oxide on the surface as compared with the conventional removing solution B. In particular, it was found that the removal of the Ni oxide film was clearly progressed in those immersed in the removing solution A for 10 minutes and 15 minutes.
【００２７】図３〜図５には、金属顕微鏡（倍率１００
０）により表面状態を調べた観察写真を示している。図
３は、酸化物除去前の表面状態であり、図４は、除去液
Ａに１５分間浸漬した後の表面状態、図５は、除去液Ｂ
に２分間浸漬した後の表面状態を示している。FIGS. 3 to 5 show a metal microscope (magnification of 100).
0) shows an observation photograph obtained by examining the surface state. FIG. 3 shows the surface state before removing the oxide, FIG. 4 shows the surface state after being immersed in the removing liquid A for 15 minutes, and FIG.
2 shows the surface state after immersion for 2 minutes.
【００２８】図５を見ると判るように、除去液Ｂに２分
間浸漬したものでは、部分的にオーバーエッチングされ
た箇所（写真中、黒く写っている部分）があり、Ｎｉめ
っき表面にクラック状のものが形成されていた。一方、
図４の除去液Ａに１５分間浸漬したものは、図５のよう
に表面が荒れている箇所は特に確認されなかった。As can be seen from FIG. 5, in the case of immersion in the removing solution B for 2 minutes, there are portions that are partially over-etched (the portions shown in black in the photograph) and cracks are formed on the Ni plating surface. Was formed. on the other hand,
In the sample immersed in the removing solution A for 15 minutes in FIG. 4, no portion having a rough surface as shown in FIG. 5 was particularly confirmed.
【００２９】また、ここで示す図３〜図５の写真の実物
はカラー写真であり、表面状態の違いを、写し出される
色の違いで判断できるもので、その結果について説明す
る。図３のカラー写真では、観察する表面全体が黄土色
に写し出されていた。この黄土色の状態はＮｉ酸化物被
膜が存在することを示していた。また、図４のカラー写
真では、観察する表面全体が灰色の状態で写し出されて
いた。この灰色の状態は、Ｎｉの金属表面が露出してい
ることを示すものであった。このことは、除去液Ａによ
りＮｉの酸化物被膜が完全に除去されていることを裏付
けるものであった。一方、図５のカラー写真では、写し
出された表面全体が、図３の酸化物除去前の状態程では
ないが、若干、薄い黄土色が写し出されていた。即ち、
除去液Ｂでは、Ｎｉの酸化物被膜の除去が不十分な状態
であることが確認された。The actual photographs shown in FIGS. 3 to 5 are color photographs, and the difference in the surface state can be determined based on the difference in the displayed color. The results will be described. In the color photograph of FIG. 3, the entire surface to be observed was projected in ocher. This ocher state indicated the presence of the Ni oxide coating. Further, in the color photograph of FIG. 4, the entire surface to be observed was projected in a gray state. This gray state indicated that the metal surface of Ni was exposed. This proved that the removing solution A completely removed the Ni oxide film. On the other hand, in the color photograph shown in FIG. 5, although the entire surface was not as bright as the state before the oxide removal shown in FIG. That is,
It was confirmed that the removal liquid B was in a state where the removal of the Ni oxide film was insufficient.
【００３０】最後に、半田濡れ性の評価を行った結果に
ついて説明する。この半田濡れ性の評価は、除去液Ａ及
びＢでＮｉ酸化物被膜を除去した評価サンプルを用い、
塩酸（５０％）による酸活性処理をした後、０．０５μ
ｍ厚さの置換Ａｕめっきを施し、溶融状態の半田を接触
させることで行った。このときの置換Ａｕめっき液は、
商品名プレシャスファブＩＧ７９０３（日本エレクトロ
プレイティング・エンジニヤース（株）製）を用いた。
半田濡れ性評価の条件は、２００℃の半田浴（６３％Ｐ
ｂ−３７Ｓｎ組成の半田浴）に３０秒間浸漬するもので
ある。半田濡れ性評価結果を表３に示す。Finally, the result of the evaluation of the solder wettability will be described. The evaluation of the solder wettability was performed using an evaluation sample from which the Ni oxide film was removed with the removal liquids A and B,
After acid activation treatment with hydrochloric acid (50%), 0.05μ
This was performed by applying a displacement Au plating having a thickness of m and bringing the molten solder into contact therewith. The replacement Au plating solution at this time is
Precious Fab IG7903 (trade name, manufactured by Nippon Electroplating Engineers, Inc.) was used.
The condition for the evaluation of the solder wettability was a solder bath at 200 ° C. (63% P
b-37Sn solder bath) for 30 seconds. Table 3 shows the results of the solder wettability evaluation.
【００３１】[0031]
【表３】 [Table 3]
【００３２】表３中、×は濡れ性が悪い状態であったこ
とを示しており、○は濡れ性が良好であったことを示し
ている。この半田濡れ性評価結果により、除去液Ａで１
０分間以上浸漬した場合、良好な半田濡れ性を示すこと
が判明した。この半田濡れ性が悪い状態となる理由は、
Ｎｉ酸化物被膜が残存すると、置換によるＡｕめっきが
Ｎｉ表面へ、均一に形成されないためである。即ち、従
来の除去液Ｂでは、図５で示したように、２分間の浸漬
時間では酸化物の除去が不完全で、Ｎｉめっきにもクラ
ックが形成され、表面が荒れた状態となる結果、半田濡
れ性は悪いものとなった。そして、除去液Ｂの浸漬時間
を更に長くしても、酸化物の除去は進行するものの、Ｎ
ｉめっき表面が非常に荒れた状態となり、結果的に半田
濡れ性の向上は図れないことが判明した。一方、除去液
Ａでは、浸漬時間を１０〜１５分にすると、Ｎｉの酸化
物被膜が十分に除去され、Ｎｉめっき表面も過度に荒れ
ることがないため、半田濡れ性評価が良好な結果となる
ことが判明した。In Table 3, x indicates that the wettability was poor, and ○ indicates that the wettability was good. According to the evaluation result of the solder wettability, 1
It was found that when immersed for 0 minutes or more, good solder wettability was exhibited. The reason for the poor solder wettability is that
This is because if the Ni oxide film remains, Au plating due to substitution is not uniformly formed on the Ni surface. That is, in the conventional removing solution B, as shown in FIG. 5, the removal of the oxide is incomplete with the immersion time of 2 minutes, cracks are formed on the Ni plating, and the surface is roughened. Solder wettability was poor. Then, even if the immersion time of the removing liquid B is further increased, the removal of the oxide proceeds, but the N
It turned out that the i-plated surface was in a very rough state, and consequently the solder wettability could not be improved. On the other hand, in the removal liquid A, when the immersion time is 10 to 15 minutes, the oxide film of Ni is sufficiently removed, and the Ni plating surface is not excessively roughened. It has been found.
【００３３】[0033]
【発明の効果】以上述べたように、本発明の金属酸化物
被膜の除去液を用いると、表面を過度に荒らすことな
く、平滑且つ均一に酸化物被膜を除去することができ、
通電操作が行えないものに対しても効率的に酸化物被膜
の除去が可能となる。As described above, the use of the metal oxide film removing solution of the present invention makes it possible to remove the oxide film smoothly and uniformly without excessively roughening the surface.
It is possible to efficiently remove the oxide film even on those that cannot be energized.
【図１】評価サンプルの断面概略図。FIG. 1 is a schematic cross-sectional view of an evaluation sample.
【図２】オージェ分析による表面深さ方向における酸素
濃度分析結果を示すグラフ。FIG. 2 is a graph showing the results of oxygen concentration analysis in the surface depth direction by Auger analysis.
【図３】Ｎｉ酸化物被膜除去前の表面観察写真。FIG. 3 is a photograph of surface observation before removing a Ni oxide film.
【図４】除去液ＡによるＮｉ酸化物被膜除去後の表面観
察写真。FIG. 4 is a photograph of a surface observation after removing a Ni oxide film with a removing solution A.
【図５】除去液ＢによるＮｉ酸化物被膜除去後の表面観
察写真。FIG. 5 is a photograph of a surface observation after removing a Ni oxide film using a removing liquid B;
１ 基板 ２ 下地導電層 ３ Ｎｉめっき ４ 絶縁膜 ５ Ｎｉ酸化物被膜 DESCRIPTION OF SYMBOLS 1 Substrate 2 Underlayer conductive layer 3 Ni plating 4 Insulating film 5 Ni oxide film
Claims (5)
を還元反応により除去する金属酸化物被膜の除去液であ
って、 アルカリ脱脂剤と還元剤とを含有する金属酸化物被膜の
除去液。1. A metal oxide film removing solution for removing a metal oxide film formed on a metal surface by a reduction reaction, comprising a metal oxide film removing solution containing an alkali degreasing agent and a reducing agent. .
酸化ナトリウム、メタケイ酸ナトリウム、リン酸塩、ケ
イ酸塩、グルコン酸塩のいずれか１種又は２種以上を用
いるものである請求項１に記載の金属酸化物被膜の除去
液。2. The method according to claim 1, wherein the alkali degreasing agent uses one or more of sodium carbonate, sodium hydroxide, sodium metasilicate, phosphate, silicate and gluconate. A liquid for removing a metal oxide film according to the above.
素化ホウ素カリウム、ジメチルアミンボランのいずれか
１種又は２種以上を用いる請求項１又は請求項２に記載
の金属酸化物被膜の除去液。3. The metal oxide film removing solution according to claim 1, wherein the reducing agent is any one or more of sodium borohydride, potassium borohydride, and dimethylamine borane. .
載する金属酸化物被膜の除去液に、金属酸化物の被膜を
有する金属を浸漬し、還元反応により発生する水素によ
って金属酸化物を還元するものである金属酸化物被膜の
除去方法。4. A metal having a metal oxide film is immersed in the metal oxide film removal solution according to any one of claims 1 to 3, and the metal is oxidized by hydrogen generated by a reduction reaction. A method for removing a metal oxide film that reduces substances.
件で還元反応を進行させるものである請求項４に記載の
金属酸化物被膜の除去方法。5. The method for removing a metal oxide film according to claim 4, wherein the reduction reaction proceeds at a pH of 10 to 14 and a liquid temperature of 10 to 80 ° C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422387C (en) * | 2006-01-11 | 2008-10-01 | 武汉钢铁(集团)公司 | Cleaning agent for pretreatment of cold-rolling galvanization |
| CN102277587A (en) * | 2011-07-29 | 2011-12-14 | 沈阳大学 | Method for removing hard multi-component nitride reaction film |
| CN103882459A (en) * | 2014-03-31 | 2014-06-25 | 沈阳大学 | Method for removing titanium chromium nitride hard reaction film |
| CN116065159A (en) * | 2023-03-22 | 2023-05-05 | 山东龙程矿业科技股份有限公司 | Environment-friendly efficient metal cleaning agent |
-
2000
- 2000-09-27 JP JP2000293449A patent/JP3906019B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422387C (en) * | 2006-01-11 | 2008-10-01 | 武汉钢铁(集团)公司 | Cleaning agent for pretreatment of cold-rolling galvanization |
| CN102277587A (en) * | 2011-07-29 | 2011-12-14 | 沈阳大学 | Method for removing hard multi-component nitride reaction film |
| CN103882459A (en) * | 2014-03-31 | 2014-06-25 | 沈阳大学 | Method for removing titanium chromium nitride hard reaction film |
| CN116065159A (en) * | 2023-03-22 | 2023-05-05 | 山东龙程矿业科技股份有限公司 | Environment-friendly efficient metal cleaning agent |
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