JP5990789B2 - Activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating - Google Patents
Activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating Download PDFInfo
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- JP5990789B2 JP5990789B2 JP2014139451A JP2014139451A JP5990789B2 JP 5990789 B2 JP5990789 B2 JP 5990789B2 JP 2014139451 A JP2014139451 A JP 2014139451A JP 2014139451 A JP2014139451 A JP 2014139451A JP 5990789 B2 JP5990789 B2 JP 5990789B2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 195
- 238000007747 plating Methods 0.000 title claims description 149
- 229910052763 palladium Inorganic materials 0.000 title claims description 97
- 230000004913 activation Effects 0.000 title claims description 51
- 229910001252 Pd alloy Inorganic materials 0.000 title claims description 41
- 239000007788 liquid Substances 0.000 title claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 238000011282 treatment Methods 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 4
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims 1
- 238000001994 activation Methods 0.000 description 49
- 239000010408 film Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- 229910000679 solder Inorganic materials 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 12
- 239000010931 gold Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Description
本発明は、無電解パラジウムめっき又は無電解パラジウム合金めっきの前処理用活性化液、及び該活性化液を用いる無電解パラジウムめっき又は無電解パラジウム合金めっき方法に関する。 The present invention relates to an activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating, and an electroless palladium plating or electroless palladium alloy plating method using the activation liquid.
従来から、エレクトロニクス関連分野において、コネクター、リードフレームなどへの機能性薄膜の形成方法として、無電解ニッケルめっき皮膜上に無電解金めっき皮膜を形成する無電解ニッケル／金めっき処理が広く応用されている。近年、プリント配線板の高密度化、表面実装基板（独立回路基板）の増加等に伴い、プリント配線板の銅回路表面の酸化を防止して良好なはんだ接続性能を発揮させることや、半導体パッケージとその上に実装される電子部品とのワイヤーボンディング性を向上させることなどを目的として、無電解ニッケルめっきを行った後、無電解パラジウムめっきを行い、その後無電解金めっきを行う、無電解ニッケル／パラジウム／金めっき処理が増加している（下記特許文献１参照）。 Conventionally, in the field of electronics, as a method of forming a functional thin film on a connector, a lead frame, etc., an electroless nickel / gold plating process for forming an electroless gold plating film on an electroless nickel plating film has been widely applied. Yes. In recent years, with the increase in the density of printed wiring boards and the increase in surface mount boards (independent circuit boards), it is possible to prevent the copper circuit surface of printed wiring boards from being oxidized and to exhibit good solder connection performance. Electroless nickel plating, followed by electroless palladium plating, followed by electroless gold plating for the purpose of improving wire bonding between the device and the electronic components mounted on it. / Palladium / gold plating treatment is increasing (see Patent Document 1 below).
今後、プリント配線板の更なるファインパターン化が予想されるが、上記した無電解ニッケル／パラジウム／金めっき処理を行う場合には、素材銅の状態や前処理（脱脂、エッチング）の程度によって、無電解パラジウムめっきの析出性が不十分となり易く、カバーリング性能が劣化してはんだ接合強度が低くなることがあるという問題点がある。 In the future, further fine patterning of printed wiring boards is expected, but when performing the above electroless nickel / palladium / gold plating treatment, depending on the state of the material copper and the degree of pretreatment (degreasing, etching), There is a problem in that the deposition property of electroless palladium plating tends to be insufficient, the covering performance is deteriorated, and the solder joint strength may be lowered.
また、セラミック基板においては、銀ペーストや銅ペーストが回路の配線に用いられており、この様な回路を形成したセラミック基板に対しても、同様に無電解ニッケル／パラジウム／金めっき工法が検討されている。この場合にも、やはり、素材の状態や前処理の影響によって無電解パラジウムめっきの析出性が低下することがある。このため、上記した材料に対しても、無電解パラジウムめっきの析出性を向上させることができる前処理方法が要求されている。 In addition, silver paste and copper paste are used for circuit wiring in ceramic substrates, and electroless nickel / palladium / gold plating methods are similarly examined for ceramic substrates on which such circuits are formed. ing. In this case as well, the depositability of the electroless palladium plating may deteriorate due to the condition of the material and the effect of the pretreatment. For this reason, the pre-processing method which can improve the depositability of electroless palladium plating is requested | required also with above-described material.
本発明は、上記した従来技術の現状に鑑みてなされてものであり、その主な目的は、無電解ニッケル皮膜や銅素材などの各種の金属材料上に無電解パラジウムめっき又は無電解パラジウム合金めっきを行う際に、良好な析出性でカバーリング性に優れたパラジウム又はパラジウム合金めっき皮膜を形成するために有用な新規な前処理剤、及び該前処理剤を用いる無電解パラジウム又はパラジウム合金めっき法を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is electroless palladium plating or electroless palladium alloy plating on various metal materials such as electroless nickel film and copper material. , A novel pretreatment agent useful for forming a palladium or palladium alloy plating film with good precipitation and excellent covering properties, and an electroless palladium or palladium alloy plating method using the pretreatment agent Is to provide.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、無電解パラジウムめっき又は無電解パラジウム合金めっきを行う前に、被処理物を還元剤を含有する水溶液に接触させた後、水洗を行うことなく、直接、無電解パラジウムめっき又は無電解パラジウム合金めっきを行う場合には、各種の金属素材上に、析出性よく、カバーリング性に優れた無電解パラジウムめっき皮膜又は無電解パラジウム合金めっき皮膜を形成する
ことが可能となることを見出し、ここに本発明を完成するに至った。
The present inventor has intensively studied to achieve the above-described object. As a result, before performing electroless palladium plating or electroless palladium alloy plating, the object to be treated is brought into contact with an aqueous solution containing a reducing agent and then directly electroless palladium plated or electroless palladium without washing. In the case of alloy plating, it has been found that an electroless palladium plating film or an electroless palladium alloy plating film with good precipitation and excellent covering properties can be formed on various metal materials. The present invention has been completed.
即ち、本発明は下記の無電解パラジウムめっき又は無電解パラジウム合金めっきの前処理用活性化液、及び該活性化液を用いる無電解パラジウムめっき又は無電解パラジウム合金めっき方法を提供するものである。
１． 還元剤を有効成分として含有する水溶液からなる、無電解パラジウムめっき又は無電解パラジウム合金めっきの前処理用活性化液。
２． 還元剤が、次亜リン酸塩、ジメチルアミンボラン、水素化ホウ素ナトリウム、亜リン酸塩及びギ酸塩からなる群から選ばれた少なくとも一種である、上記項１に記載の無電解パラジム又はパラジウム合金めっきの前処理用活性化液。
３． 被処理物の処理対象部分が金属材料である、上記項１又は２に記載の無電解パラジム又はパラジウム合金めっきの前処理用活性化液。
４． 上記項１〜３のいずれかに記載の無電解パラジウムめっき又は無電解パラジウム合金めっきの前処理用活性化液を被処理物に接触させた後、水洗を行うことなく、無電解パラジウムめっき又は無電解パラジウム合金めっきを行うことを特徴とする無電解パラジウムめっき又は無電解パラジウム合金めっき方法。
That is, the present invention provides an activation liquid for pretreatment of the following electroless palladium plating or electroless palladium alloy plating, and an electroless palladium plating or electroless palladium alloy plating method using the activation liquid.
1. An activation liquid for pretreatment of electroless palladium plating or electroless palladium alloy plating, comprising an aqueous solution containing a reducing agent as an active ingredient.
2. The electroless paradymium or palladium alloy according to Item 1, wherein the reducing agent is at least one selected from the group consisting of hypophosphite, dimethylamine borane, sodium borohydride, phosphite and formate. Activation liquid for plating pretreatment.
3. Item 3. The activation liquid for pretreatment of electroless paradium or palladium alloy plating according to Item 1 or 2, wherein the treatment target portion of the workpiece is a metal material.
4). The electroless palladium plating or electroless palladium plating or electroless palladium alloy plating pretreatment activation liquid according to any one of the above items 1 to 3 is brought into contact with an object to be treated, and then washed with water without washing. Electroless palladium plating or electroless palladium alloy plating method, characterized by performing electrolytic palladium alloy plating.
以下、本発明の無電解パラジウムめっき又は無電解パラジウム合金めっきの前処理用活性化液について、具体的に説明する。 Hereinafter, the pretreatment activation liquid for electroless palladium plating or electroless palladium alloy plating of the present invention will be specifically described.
前処理用活性化液
本発明の無電解パラジウム又はパラジウムめっきの前処理用活性化液は、還元剤を有効成分として含有する水溶液である。
Pretreatment activation liquid The electrolysis palladium or palladium plating pretreatment activation liquid of the present invention is an aqueous solution containing a reducing agent as an active ingredient.
還元剤としては、還元作用を有する水溶性化合物であれば、特に限定無く使用できる。特に、自己触媒型の無電解めっき液に配合される還元剤であれば、後工程で用いる無電解パラジウムめっき浴又は無電解パラジウム合金めっき浴に対する悪影響が少ない点から好適であり、後工程で用いる無電解パラジウムめっき浴又は無電解パラジウム合金めっき浴に配合される還元剤と同一の還元剤を用いることが特に好ましい。 As the reducing agent, any water-soluble compound having a reducing action can be used without particular limitation. In particular, a reducing agent blended in an autocatalytic electroless plating solution is suitable because it has little adverse effect on the electroless palladium plating bath or electroless palladium alloy plating bath used in the post-process, and is used in the post-process. It is particularly preferable to use the same reducing agent as that used in the electroless palladium plating bath or electroless palladium alloy plating bath.
この様な還元剤の具体例としては、次亜リン酸塩（アンモニウム、カリウム、ナトリウム塩など）、ジメチルアミンボラン、水素化ホウ素ナトリウム、亜リン酸塩（アンモニウム、カリウム、アンモニウム塩など）、ギ酸塩（アンモニウム、ナトリウム、カリウム、カルシウム塩など）等を挙げることができる。これらの還元剤は、一種単独又は二種以上混合して用いることができる。 Specific examples of such reducing agents include hypophosphites (ammonium, potassium, sodium salts, etc.), dimethylamine borane, sodium borohydride, phosphites (ammonium, potassium, ammonium salts, etc.), formic acid. Examples thereof include salts (ammonium, sodium, potassium, calcium salts, etc.). These reducing agents can be used singly or in combination of two or more.
本発明の活性化液における還元剤の濃度については特に限定はないが、例えば、０．０５〜２００ｇ／Ｌ程度とすることが好ましく、０．１〜１５０ｇ／Ｌ程度とすることがより好ましい。還元剤の濃度が低すぎる場合には、無電解パラジウムめっきの析出性を向上させる効果が十分には発揮されず、一方、還元剤の濃度が高すぎる場合には、特に問題はないが、使用量の増加に見合う効果が得られないので、不経済である。 Although there is no limitation in particular about the density | concentration of the reducing agent in the activation liquid of this invention, For example, it is preferable to set it as about 0.05-200 g / L, and it is more preferable to set it as about 0.1-150 g / L. If the concentration of the reducing agent is too low, the effect of improving the deposition properties of the electroless palladium plating is not sufficiently exhibited. On the other hand, if the concentration of the reducing agent is too high, there is no problem. Since an effect commensurate with the increase in amount cannot be obtained, it is uneconomical.
本発明の活性化液のｐＨについては、特に限定はないが、水洗を行うことなく、引き続き無電解パラジウムめっき又は無電解パラジウム合金めっきを行うので、使用するめっき液のｐＨに近いｐＨ値とすることが好ましい。 The pH of the activation liquid of the present invention is not particularly limited. However, since electroless palladium plating or electroless palladium alloy plating is subsequently performed without washing with water, the pH value is close to the pH of the plating liquid to be used. It is preferable.
本発明の活性化液には、該活性化液の特性に悪影響を及ぼさない限り、他の成分が含まれていてもよい。例えば、界面活性剤を添加することによって、被処理物に対する活性化液の濡れ性を向上させて、処理効率を上げることができる。 The activation liquid of the present invention may contain other components as long as the characteristics of the activation liquid are not adversely affected. For example, by adding a surfactant, the wettability of the activation liquid with respect to the object to be processed can be improved and the processing efficiency can be increased.
活性化処理方法
（ｉ）被処理物
本発明の活性化液は、金属材料上に無電解パラジウムめっき又は無電解パラジウム合金めっきを行う際に、前処理として行う活性化処理に用いるものである。
Activation treatment method (i) Object to be treated The activation liquid of the present invention is used for an activation treatment performed as a pretreatment when performing electroless palladium plating or electroless palladium alloy plating on a metal material.
処理対象の金属材料の種類については特に限定はなく、その具体例としては、プリント配線板における銅などの導体回路部分、セラミック基板における銀ペースト、銅ペースト、金ペースト、白金ペースト、タングステンペースト、モリブデンペーストなどによる配線部分、無電解ニッケル／パラジウム／金めっき処理を行う際の無電解ニッケルめっき皮膜などを挙げることができる。 There are no particular limitations on the type of metal material to be processed, and specific examples include conductor circuit parts such as copper in printed wiring boards, silver paste, copper paste, gold paste, platinum paste, tungsten paste, and molybdenum on ceramic substrates. Examples thereof include a wiring portion made of paste or the like, and an electroless nickel plating film when electroless nickel / palladium / gold plating is performed.
（ii）処理工程
本発明の活性化液による活性化処理は、被処理物を本発明の活性化液に接触させるこ
とによって行うことができる。
(Ii) Treatment step The activation treatment with the activation liquid of the present invention can be carried out by bringing an object to be treated into contact with the activation liquid of the present invention.
具体的な接触方法については特に限定はなく、例えば、本発明の活性化液を被処理物に噴霧する方法でもよいが、通常は、本発明の活性化液中に被処理物を浸漬する方法によれば、効率のよい処理が可能である。 The specific contact method is not particularly limited, and for example, the method of spraying the activation liquid of the present invention onto the object to be treated may be used, but usually the method of immersing the object of treatment in the activation liquid of the present invention. According to the above, efficient processing is possible.
浸漬法によって処理を行う場合には、例えば、２０〜８０℃程度の活性化液中に、被処理物を３０秒〜１０分程度浸漬すればよい。 In the case of performing the treatment by the dipping method, for example, the treatment object may be dipped in an activation solution at about 20 to 80 ° C. for about 30 seconds to 10 minutes.
尚、被処理物については、本発明の活性化液による処理に先立って、通常の前処理を行うことができる。例えば、必要に応じて、脱脂、エッチングなどの処理を行うことができる。また、無電解パラジウムめっきに対して触媒活性のない金属を被処理物とする場合には、センシタイザー・アクチベーター法、キャタリスト法などの公知の方法によって、Pd等の触媒を付与した後、本発明の活性化液による活性化処理を行えばよい。 In addition, about a to-be-processed object, a normal pre-process can be performed prior to the process by the activation liquid of this invention. For example, treatments such as degreasing and etching can be performed as necessary. In addition, when a metal having no catalytic activity for electroless palladium plating is to be treated, after applying a catalyst such as Pd by a known method such as a sensitizer / activator method or a catalyst method, What is necessary is just to perform the activation process by the activation liquid of this invention.
（iv）無電解パラジウムめっき又は無電解パラジウム合金めっき工程
上記した方法で本発明の活性化液による活性化処理を行った後、水洗を行うことなく、直接、無電解パラジウムめっき又は無電解パラジウム合金めっきを行う。これにより、良好な析出性でカバーリング性に優れたパラジウム又はパラジウム合金めっき皮膜を形成することができる。また、本発明の活性化液を用いることによって、銅素材上に直接無電解パラジウムめっき又は無電解パラジウム合金めっきを行う際にも、良好なパラジウム又はパラジウム合金めっき皮膜を形成することができる。
(Iv) Electroless palladium plating or electroless palladium alloy plating step After performing the activation treatment with the activation liquid of the present invention by the above-described method, the electroless palladium plating or the electroless palladium alloy is directly performed without washing with water. Plating is performed. Thereby, it is possible to form a palladium or palladium alloy plating film having excellent precipitation and excellent covering properties. Further, by using the activation liquid of the present invention, a good palladium or palladium alloy plating film can be formed even when electroless palladium plating or electroless palladium alloy plating is directly performed on a copper material.
この方法で形成される無電解パラジウムめっき皮膜又はパラジウム合金めっき皮膜は、従来の方法で得られる皮膜と比較して、ピンホールが少ない良好なめっき皮膜であり、はんだ接合強度が高い皮膜となる。銀ペーストや銅ペーストによる導体回路を形成したセラミック基板に処理を行う場合にも、良好な析出性やはんだ接合強度を得ることが出来る。 The electroless palladium plating film or palladium alloy plating film formed by this method is a good plating film with few pinholes and a film with high solder joint strength as compared with a film obtained by a conventional method. Even when processing is performed on a ceramic substrate on which a conductor circuit is formed using silver paste or copper paste, good precipitation and solder joint strength can be obtained.
本発明において使用できる無電解パラジウムめっき浴及び無電解パラジウム合金めっき浴の種類については特に限定はなく、還元剤を含有する自己触媒型の無電解パラジウムめっき浴又は無電解パラジウム合金めっき浴であればよい。還元剤の種類についても特に限定はなく、次亜リン酸塩、ジメチルアミンボラン、水素化ホウ素ナトリウム、亜リン酸塩、ギ酸塩等を還元剤として含む公知の無電解パラジウムめっき浴又は無電解パラジウム合金めっき浴を用いることができる。パラジウム合金としては、例えば、Ｐｄ−Ｐ、Ｐｄ−Ｂ、Ｐｄ−Ｎｉ等を挙げることができる。 There are no particular limitations on the type of electroless palladium plating bath and electroless palladium alloy plating bath that can be used in the present invention, so long as it is a self-catalyzed electroless palladium plating bath or electroless palladium alloy plating bath containing a reducing agent. Good. There is no particular limitation on the type of reducing agent, and a known electroless palladium plating bath or electroless palladium containing hypophosphite, dimethylamine borane, sodium borohydride, phosphite, formate, etc. as a reducing agent. An alloy plating bath can be used. Examples of the palladium alloy include Pd—P, Pd—B, and Pd—Ni.
無電解パラジウムめっき又は無電解パラジウム合金めっきの条件については、特に限定
はなく、具体的に使用するめっき浴の組成に応じて、公知の条件から適宜決めればよい。
The conditions for electroless palladium plating or electroless palladium alloy plating are not particularly limited, and may be appropriately determined from known conditions according to the composition of the plating bath to be specifically used.
無電解パラジウムめっき又は無電解パラジウム合金めっきを行った後、必要に応じて、公知の方法に従って、例えば、無電解金めっき処理などを行うことができる。 After performing electroless palladium plating or electroless palladium alloy plating, for example, electroless gold plating can be performed according to a known method, if necessary.
本発明の活性化剤を用いて各種の金属材料に対して活性化処理を行うことによって、無電解パラジウムめっき又は無電解パラジウム合金めっきの析出性を改善して、カバーリング性を向上させることができる。これにより、銅回路上や銀ペースト、銅ペーストなどからなる配線部分に、良好なパラジウム又はパラジウム合金めっき皮膜を形成することが可能となる。また、無電解ニッケルめっき皮膜上に無電解パラジウム又は無電解パラジウム合金めっき皮膜を形成する際にも良好なパラジウム又はパラジウム合金めっき皮膜を形成することが可能となる。これにより、半導体パッケージや回路部分などに対するワイヤーボンディング性、ハンダ接続性能などを改善して、優れた性能を有する電子部品を製造することが可能となる。 By performing activation treatment on various metal materials using the activator of the present invention, it is possible to improve the deposition property of electroless palladium plating or electroless palladium alloy plating and improve the covering property. it can. This makes it possible to form a favorable palladium or palladium alloy plating film on the copper circuit or on the wiring portion made of silver paste, copper paste, or the like. In addition, when forming an electroless palladium or electroless palladium alloy plating film on the electroless nickel plating film, a good palladium or palladium alloy plating film can be formed. Thereby, it becomes possible to improve the wire bonding property, solder connection performance, etc. with respect to a semiconductor package or a circuit part, and to manufacture the electronic component which has the outstanding performance.
以下、実施例を挙げて本発明を更に詳細に説明する。
実施例１
被処理物として、樹脂基材上に、銅によるパッド部（ＢＧＡパターン）を形成した独立回路基板を用いた。図１に被処理物の概略の平面図を示す。パッド部の径は、０．２ｍｍと０．６ｍｍの２種類である。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
As an object to be processed, an independent circuit board in which a pad portion (BGA pattern) made of copper was formed on a resin base material was used. FIG. 1 shows a schematic plan view of an object to be processed. There are two types of diameters of the pad portion: 0.2 mm and 0.6 mm.
まず、上記した被処理物に対して、樹脂基板用の前処理剤を用いて、脱脂、エッチング及びパラジウム触媒の付与を行い、次いで、市販の無電解ニッケルめっき液（奥野製薬工業製：ＩＣＰニコロンＳＯＦ）を用いて、厚さ約５μｍのニッケルめっき皮膜を形成した。 First, degreasing, etching, and application of a palladium catalyst are performed on the object to be processed using a pretreatment agent for a resin substrate, and then a commercially available electroless nickel plating solution (Okuno Pharmaceutical Co., Ltd .: ICP Nicolon). Using SOF), a nickel plating film having a thickness of about 5 μm was formed.
次いで、下記表１及び表２に示す各活性化液に１分間浸漬後、水洗を行うことなく、表３に示す無電解パラジウムめっき液に浸漬して、厚さ約０．２μｍのパラジウムめっき皮膜を形成した。 Next, after immersing in each of the activation liquids shown in Tables 1 and 2 for 1 minute, without being washed with water, it was immersed in an electroless palladium plating solution shown in Table 3 to give a palladium plating film having a thickness of about 0.2 μm. Formed.
一方、比較試験として、上記した方法と同様にして無電解ニッケルめっきを５μｍ施した後、水洗を１分間行い、活性化処理を行うことなく、表３に示す無電解パラジウムめっき液に直接浸漬して、パラジウムめっき皮膜を０．２μｍ形成した。 On the other hand, as a comparative test, 5 μm of electroless nickel plating was applied in the same manner as described above, followed by washing with water for 1 minute and directly immersing in the electroless palladium plating solution shown in Table 3 without performing activation treatment. Thus, 0.2 μm of a palladium plating film was formed.
以上の試験は、樹脂基材の銅パッド部分に形成したニッケルめっき皮膜上に、無電解パラジウムめっきを行う際の本発明の活性化液の有効性を評価するものである。 The above test evaluates the effectiveness of the activation liquid of the present invention when electroless palladium plating is performed on a nickel plating film formed on a copper pad portion of a resin base material.
上記した方法で得られた各試料について、下記の方法で無電解パラジウムめっき皮膜の外観、析出性及びはんだ接合強度を評価した。結果を下記表４に示す。
（１）析出外観
目視によりパラジウムめっき皮膜の外観を評価した。
（２）析出性
パッド径０．６ｍｍのＢＧＡ搭載用パターン部分について、パッド２０個当たりの無電解パラジウムめっきが析出した個数を目視でカウントして、析出性を評価した。
（３）はんだ接合強度
パッド径０．６ｍｍのＢＧＡ搭載用パターン部分について、無電解パラジウムめっき皮膜上に、市販の無電解金めっき液（奥野製薬工業製：フラッシュゴールド３３０）を用いて厚さ約０．０３μｍの金めっき皮膜を形成した。その後、Ｓｎ−３Ａｇ−０．５Ｃｕのはんだボールを搭載し、リフロー装置にて加熱した後、常温式はんだボールプル試験装置を用いてはんだ接合強度を測定した。１条件につき２０個測定し、その平均値で評価を行った。尚、活性化処理を行っていない試験片については、無電解パラジウムめっきが析出した箇所についてのみ上記した方法ではんだ接合強度を測定した。
About each sample obtained by the above-mentioned method, the external appearance, precipitation property, and solder joint strength of the electroless palladium plating film were evaluated by the following method. The results are shown in Table 4 below.
(1) Precipitation appearance The appearance of the palladium plating film was visually evaluated.
(2) Precipitation About the pattern part for BGA mounting with a 0.6 mm diameter pad diameter, the number of electroless palladium plating deposits per 20 pads was visually counted to evaluate the precipitation.
(3) Solder joint strength About a BGA mounting pattern part with a pad diameter of 0.6 mm, a commercially available electroless gold plating solution (manufactured by Okuno Pharmaceutical Co., Ltd .: Flash Gold 330) is used on the electroless palladium plating film. A 0.03 μm gold plating film was formed. Then, after mounting a solder ball of Sn-3Ag-0.5Cu and heating with a reflow device, the solder joint strength was measured using a room temperature type solder ball pull test device. Twenty pieces were measured per condition, and the average value was evaluated. In addition, about the test piece which has not performed the activation process, the solder joint strength was measured by the above-mentioned method only about the location which electroless palladium plating deposited.
実施例２
実施例１で用いたものと同じ銅によるパッド部（ＢＧＡパターン）を形成した独立回路基板を被処理物として用い、実施例１と同様にして、樹脂基板用の前処理剤を用いて脱脂、エッチング及びパラジウム触媒付与を行った後、無電解ニッケルめっきを行うことなく、上記表１及び表２に示す実施例１で用いた各活性化液に１分間浸漬後、水洗を行うことなく、表３に示す無電解パラジウムめっき液に浸漬して、厚さ約０．２μｍのパラジウムめっき皮膜を形成した。
Example 2
Using an independent circuit board in which the same pad portion (BGA pattern) made of copper as that used in Example 1 was formed as an object to be processed, degreasing using a pretreatment agent for a resin substrate as in Example 1 After performing etching and palladium catalyst application, without electroless nickel plating, after immersion for 1 minute in each activation solution used in Example 1 shown in Tables 1 and 2 above, without washing with water, 3 was immersed in an electroless palladium plating solution to form a palladium plating film having a thickness of about 0.2 μm.
一方、比較試験として、上記した方法と同様にして脱脂、エッチング及びパラジウム触媒付与を行った後、活性化処理を行うことなく、表３に示す無電解パラジウムめっき液に直接浸漬して、パラジウムめっき皮膜を０．２μｍ形成した。 On the other hand, as a comparative test, after degreasing, etching and applying a palladium catalyst in the same manner as described above, the palladium plating was performed by directly immersing in the electroless palladium plating solution shown in Table 3 without performing the activation treatment. A film having a thickness of 0.2 μm was formed.
以上の試験は、樹脂基材の銅パッド部分に直接無電解パラジウムめっきを行う際の本発明の活性化液の有効性を評価するものである。 The above test evaluates the effectiveness of the activation liquid of the present invention when performing electroless palladium plating directly on the copper pad portion of the resin substrate.
実施例１と同様にして、無電解パラジウムめっき皮膜の外観、析出性、及びはんだ接合強度を評価した。結果を下記表５に示す。 In the same manner as in Example 1, the appearance, depositability, and solder joint strength of the electroless palladium plating film were evaluated. The results are shown in Table 5 below.
以上の実施例１及び実施例２の結果から明らかなように、ＢＧＡ基板に対して、無電解ニッケルめっきを行った後、無電解パラジウムめっきを行う場合及びＢＧＡ基板の銅素材上に直接無電解パラジウムめっきを行う場合のいずれの場合にも、無電解パラジウムめっきを行う前に、本発明の活性化液を用いて活性化処理を行うことによって、無電解パラジウムめっき皮膜の外観及び析出性が良好となり、はんだ接合強度についても向上することが確認できた。 As is clear from the results of Examples 1 and 2 above, the electroless nickel plating is performed on the BGA substrate, and then electroless palladium plating is performed. In any case of performing palladium plating, before the electroless palladium plating is performed, the appearance and precipitation of the electroless palladium plating film is good by performing the activation treatment using the activation liquid of the present invention. Thus, it was confirmed that the solder joint strength was also improved.
実施例３
被処理物として、セラミックスからなる基材上に、印刷法によって銀ペーストによるパターンを形成した基板を用いた。図２に被処理物の概略の平面図を示す。
Example 3
As the object to be processed, a substrate in which a pattern made of silver paste was formed on a base material made of ceramics by a printing method was used. FIG. 2 shows a schematic plan view of the workpiece.
まず、上記した被処理物に対して、セラミックス用の前処理剤を用いて、脱脂、エッチング及びパラジウム触媒の付与を行い、次いで、市販の無電解ニッケルめっき液（奥野製薬工業製：ＮＮＰニコロンＬＴＣ）を用いて、厚さ約５μｍのニッケルめっき皮膜を形成した。 First, degreasing, etching, and application of a palladium catalyst are performed on the above-described object to be processed using a pretreatment agent for ceramics, and then a commercially available electroless nickel plating solution (Okuno Pharmaceutical Co., Ltd .: NNP Nicolon LTC) ) Was used to form a nickel plating film having a thickness of about 5 μm.
次いで、上記表１及び表２に示す実施例１で用いた各活性化液に１分間浸漬後、水洗を行うことなく、実施例１の表３に示す無電解パラジウムめっき液に浸漬して、厚さ約０．２μｍのパラジウムめっき皮膜を形成した。 Next, after immersing in each activation solution used in Example 1 shown in Table 1 and Table 2 for 1 minute, without rinsing, it was immersed in the electroless palladium plating solution shown in Table 3 of Example 1, A palladium plating film having a thickness of about 0.2 μm was formed.
一方、比較試験として、上記した方法と同様にして無電解ニッケルめっきを５μｍ施した後、水洗を１分間行い、活性化処理を行うことなく、表３に示す無電解パラジウムめっき液に浸漬して、パラジウムめっき皮膜を０．２μｍ形成した。 On the other hand, as a comparative test, 5 μm of electroless nickel plating was applied in the same manner as described above, followed by washing with water for 1 minute and immersion in the electroless palladium plating solution shown in Table 3 without performing activation treatment. Then, 0.2 μm of a palladium plating film was formed.
以上の試験は、セラミック基材上の銀ペーストによるパターン部分に形成したニッケルめっき皮膜上に、無電解パラジウムめっきを行う際の本発明の活性化液の有効性を評価するものである。 The above test evaluates the effectiveness of the activation liquid of the present invention when electroless palladium plating is performed on a nickel plating film formed on a pattern portion of a silver paste on a ceramic substrate.
上記した方法で得られた各試料について、実施例１と同様にして、パラジウムめっき皮膜の析出外観及び析出性を評価した。析出性については、パッド２０個当たりの無電解パラジウムめっきが析出した個数を目視でカウントして評価した。結果を下記表６に示す。 About each sample obtained by the above-mentioned method, it carried out similarly to Example 1, and evaluated the precipitation external appearance and precipitation property of the palladium plating film. Precipitation was evaluated by visually counting the number of deposits of electroless palladium plating per 20 pads. The results are shown in Table 6 below.
実施例４
実施例３で用いたものと同じ銀ペーストによるパターンを有する基板を被処理物として用い、実施例３と同様にして、セラミックス用の前処理剤を用いて脱脂、エッチング及びパラジウム触媒付与を行った後、無電解ニッケルめっきを行うことなく、上記表１及び表２に示す各活性化液に１分間浸漬後、水洗を行うことなく、表３に示す無電解パラジウムめっき液に浸漬して、厚さ約０．２μｍのパラジウムめっき皮膜を形成した。
Example 4
A substrate having the same silver paste pattern as used in Example 3 was used as an object to be processed, and degreasing, etching, and palladium catalyst application were performed using a pretreatment agent for ceramics in the same manner as in Example 3. Then, after immersing in each activation solution shown in Table 1 and Table 2 for 1 minute without performing electroless nickel plating, and immersing in electroless palladium plating solution shown in Table 3 without washing with water, A palladium plating film having a thickness of about 0.2 μm was formed.
一方、比較試験として、上記した方法と同様にして脱脂、エッチング及びパラジウム触媒付与を行った後、活性化処理を行うことなく、表３に示す無電解パラジウムめっき液に直接浸漬して、パラジウムめっき皮膜を０．２μｍ形成した。 On the other hand, as a comparative test, after degreasing, etching and applying a palladium catalyst in the same manner as described above, the palladium plating was performed by directly immersing in the electroless palladium plating solution shown in Table 3 without performing the activation treatment. A film having a thickness of 0.2 μm was formed.
以上の試験は、セラミックス基材上に形成した銀ペーストパターン部分に直接無電解パラジウムめっきを行う際の本発明の活性化液の有効性を評価するものである。 The above test evaluates the effectiveness of the activation liquid of the present invention when performing electroless palladium plating directly on the silver paste pattern portion formed on the ceramic substrate.
実施例３と同様にして、無電解パラジウムめっき皮膜の外観及び析出性を評価した。結果を下記表７に示す。 In the same manner as in Example 3, the appearance and depositability of the electroless palladium plating film were evaluated. The results are shown in Table 7 below.
以上の実施例３及び実施例４の結果から明らかなように、セラミックス基材上に形成した銀ペーストパターン部分に対して、無電解ニッケルめっきを行った後、無電解パラジウムめっきを行う場合及び銀ペーストパターン部分に直接無電解パラジウムめっきを行う場合のいずれの場合にも、無電解パラジウムめっきを行う前に、本発明の活性化液を用いて活性化処理を行うことによって、無電解パラジウムめっき皮膜の外観及び析出性が良好となることが判る。 As is clear from the results of Example 3 and Example 4 above, the electroless nickel plating is performed on the silver paste pattern portion formed on the ceramic substrate, and then the electroless palladium plating is performed. In any case where the electroless palladium plating is directly applied to the paste pattern portion, the electroless palladium plating film is obtained by performing the activation treatment using the activation liquid of the present invention before the electroless palladium plating. It turns out that the external appearance and precipitation of this are good.
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| JP4812296B2 (en) * | 2004-12-24 | 2011-11-09 | イビデン株式会社 | Printed wiring board and printed wiring board manufacturing method |
| JP4606894B2 (en) * | 2005-02-08 | 2011-01-05 | 富士フイルム株式会社 | Metal pattern forming method, metal pattern, printed wiring board using the same, and TFT wiring circuit |
| JP2008109087A (en) * | 2006-09-28 | 2008-05-08 | Hitachi Chem Co Ltd | Substrate for mounting semiconductor chip, and preprocessing liquid |
| JP2008184679A (en) * | 2007-01-31 | 2008-08-14 | Okuno Chem Ind Co Ltd | Activation composition for electroless palladium plating |
| JP2009155668A (en) * | 2007-12-25 | 2009-07-16 | Hitachi Chem Co Ltd | Pretreatment liquid for promoting starting of electroless palladium plating reaction, electroless plating method using the pretreatment liquid, connection terminal formed by the electroless plating method, and semiconductor package using the connection terminal and its manufacturing method |
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