JP5843249B2 - 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 - Google Patents
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 Download PDFInfo
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- JP5843249B2 JP5843249B2 JP2010096149A JP2010096149A JP5843249B2 JP 5843249 B2 JP5843249 B2 JP 5843249B2 JP 2010096149 A JP2010096149 A JP 2010096149A JP 2010096149 A JP2010096149 A JP 2010096149A JP 5843249 B2 JP5843249 B2 JP 5843249B2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 209
- 238000007747 plating Methods 0.000 title claims description 159
- 229910052763 palladium Inorganic materials 0.000 title claims description 104
- 230000004913 activation Effects 0.000 title claims description 51
- 229910001252 Pd alloy Inorganic materials 0.000 title claims description 46
- 239000007788 liquid Substances 0.000 title claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000007769 metal material Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 238000001994 activation Methods 0.000 description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 43
- 239000010408 film Substances 0.000 description 39
- 229910052759 nickel Inorganic materials 0.000 description 21
- 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
- 238000005238 degreasing Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 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
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 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
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 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
- 239000008139 complexing agent Substances 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
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Description
1. 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1種の還元剤を有効成分として含有し、かつ錯化剤を含有しない水溶液からなる、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であって、被処理物の処理対象部分が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用の触媒が付与された金属材料である、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. 上記項1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であって、当該被処理物の処理対象部分が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用の触媒が付与された金属材料である、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。
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。
(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。
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。
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。
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。
(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。
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。
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。
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。
Claims (2)
- (1)亜リン酸塩のみ、(2)ギ酸塩のみ、又は(3)亜リン酸塩、次亜リン酸塩及びギ酸塩からなる還元剤を0.05〜200g/L含有し、かつ錯化剤を含有しない水溶液からなる、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であって、被処理物の処理対象部分が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用の触媒が付与された金属材料である、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。
- 請求項1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であって、当該被処理物の処理対象部分が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用の触媒が付与された金属材料である、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。
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JP2010096149A JP5843249B2 (ja) | 2010-04-19 | 2010-04-19 | 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 |
KR1020110035684A KR101719180B1 (ko) | 2010-04-19 | 2011-04-18 | 무전해 팔라듐 도금 또는 무전해 팔라듐 합금 도금의 전처리용 활성화액 |
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KR20130055956A (ko) * | 2011-11-21 | 2013-05-29 | 삼성전기주식회사 | 무전해 팔라듐 도금액 |
JP7149061B2 (ja) * | 2017-10-06 | 2022-10-06 | 上村工業株式会社 | 無電解パラジウムめっき液 |
JP7185999B2 (ja) | 2017-10-06 | 2022-12-08 | 上村工業株式会社 | 無電解パラジウムめっき液 |
KR102041850B1 (ko) | 2019-04-08 | 2019-11-06 | (주)엠케이켐앤텍 | 인쇄회로기판의 구리표면에 무전해 팔라듐 도금을 실시하기 위한 전처리 공정으로 금스트라이크 도금방법, 도금액 조성물 및 전처리 후의 무전해 팔라듐 도금과 무전해 금도금 방법 |
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JP4508380B2 (ja) * | 2000-08-23 | 2010-07-21 | イビデン株式会社 | 多層プリント配線板の製造方法 |
JP2008184679A (ja) * | 2007-01-31 | 2008-08-14 | Okuno Chem Ind Co Ltd | 無電解パラジウムめっき用活性化組成物 |
JP5286893B2 (ja) * | 2007-04-27 | 2013-09-11 | 日立化成株式会社 | 接続端子、接続端子を用いた半導体パッケージ及び半導体パッケージの製造方法 |
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