JP2020105543A - 置換金めっき液および置換金めっき方法 - Google Patents
置換金めっき液および置換金めっき方法 Download PDFInfo
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 193
- 239000010931 gold Substances 0.000 title claims abstract description 193
- 238000007747 plating Methods 0.000 title claims abstract description 184
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000007654 immersion Methods 0.000 title abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 127
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000010410 layer Substances 0.000 claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 62
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 51
- -1 gold cyanide compound Chemical class 0.000 claims abstract description 35
- 230000007797 corrosion Effects 0.000 claims abstract description 31
- 238000005260 corrosion Methods 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 150000003476 thallium compounds Chemical class 0.000 claims abstract description 15
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims description 93
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 14
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052716 thallium Inorganic materials 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002343 gold Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 150000002940 palladium Chemical class 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 2
- 239000010408 film Substances 0.000 description 79
- 239000000243 solution Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006467 substitution reaction Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 15
- 238000000151 deposition Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000010953 base metal Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006179 pH buffering agent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- UESISTHQAYQMRA-UHFFFAOYSA-M formyloxythallium Chemical compound [Tl+].[O-]C=O UESISTHQAYQMRA-UHFFFAOYSA-M 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- HQOJMTATBXYHNR-UHFFFAOYSA-M thallium(I) acetate Chemical compound [Tl+].CC([O-])=O HQOJMTATBXYHNR-UHFFFAOYSA-M 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
(実施例1〜15)
テストピースは、ガラス繊維で強化されたエポキシ樹脂製の実装基板(30mm×20mm×厚さ1mm)を使用して、次のように行った。なお、この実装基板の表面には、独立した銅パッド(0.4mm×0.4mm□,0.8mm×0.8mm□,3.0mm×3.0mm□)と銅回路(100μm幅)で接続された銅パッド(0.4mm×0.4mm□,0.8mm×0.8mm□,3.0mm×3.0mm□)が形成されている。
なお「液安定性」について、置換金めっき終了後の置換金めっき液を目視で観察して、金沈殿物と容器内壁への金析出がないものを丸印(〇)で、金沈殿物と容器内壁への金析出が観察されたものをバツ印(×)で評価した。
図1は、実施例2の置換金めっき層のみを剥離して、下地金属の表面を露呈させたものである。パラジウムめっき皮膜に形成した細かな粒界(0.5μm×0.5μm)と下層のニッケルめっき皮膜に形成した略四角形の大きな粒界(5μm×5μm)が観察される。置換金めっきは、液中の金イオンと金よりも卑な下地金属との電位差によって進行するので、これらの粒界模様は下地金属が置換反応によって腐食された痕跡を示すものである。パラジウムめっき皮膜にも、細かな腐食パターンが観察されることから、実施例2の置換金めっき液では、パラジウムめっき皮膜が全面で比較的均一に置換されたことが示唆される。パラジウムめっき皮膜が腐食された分だけ相対的にニッケルめっき皮膜の腐食が少なくなるため、ニッケルめっき皮膜に形成した略四角形の大きな粒界は、これまでの置換金めっき液から得られたものよりも、不明確で薄くなっていた。
実施例1と同様にして、表3に示す液組成と条件で比較例1〜5の置換金めっきを行った。すなわち、実施例1と同様のテストピースを使用して前処理を行い、パラジウム中間層/ニッケル中間層の積層構造を形成した後、表3に示す比較例1〜5のシアン系置換金めっき液組成と条件で置換金めっきを行った。
Claims (8)
- シアン化金化合物およびタリウム化合物を含むシアン系置換金めっき液において、pHが2.0〜4.4であること、および水酸基を有するアミノカルボン酸系キレート剤を含有することを特徴とする置換金めっき液。
- 前記のタリウム化合物がタリウムイオンとして0.1〜100mg/L、並びに、水酸基を有するアミノカルボン酸系キレート剤が0.1〜100g/Lであることを特徴とする請求項1に記載の置換金めっき液。
- 前記の水酸基を有するアミノカルボン酸系キレート剤が、HEDTAであることを特徴とする請求項1または2に記載の置換金めっき液。
- 前記のpHが2.2〜4.0であることを特徴とする請求項1〜3のいずれかに記載の置換金めっき液。
- 腐食抑制剤として、ポリエチレングリコール(平均分子量200〜20000)、アミド硫酸またはアミド硫酸塩の少なくとも1種以上を更に含み、その濃度がそれぞれ0.1〜100g/Lであることを特徴とする請求項1〜4のいずれかに記載の置換金めっき液。
- pH緩衝剤として、リン酸、グリシン、シアノ酢酸、マロン酸、フタル酸、クエン酸、ギ酸、グリコール酸、乳酸、コハク酸、酢酸、酪酸、プロピオン酸、およびそれらの塩の少なくとも1種以上を更に含むことを特徴とする請求項1〜5のいずれかに記載の置換金めっき液。
- 請求項1〜請求項6のいずれかに記載の置換金めっき液を用いて、銅、ニッケル、パラジウムのいずれかの中間層上、またはそれらの中間層からなる積層構造上に金表層を形成することを特徴とする置換金めっき方法。
- 前記積層構造は、銅金属上に無電解ニッケルめっき皮膜を形成し、更に無電解パラジウムめっき皮膜を形成した中間層の積層構造であることを特徴とする請求項7に記載の置換金めっき方法。
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JP2018242386A JP6521553B1 (ja) | 2018-12-26 | 2018-12-26 | 置換金めっき液および置換金めっき方法 |
TW108141249A TW202033827A (zh) | 2018-12-26 | 2019-11-13 | 置換金鍍覆液及置換金鍍覆方法 |
KR1020190174476A KR20200080185A (ko) | 2018-12-26 | 2019-12-24 | 치환 금도금액 및 치환 금도금 방법 |
CN201911362917.5A CN111378962A (zh) | 2018-12-26 | 2019-12-26 | 置换金镀覆液及置换金镀覆方法 |
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JP2018242386A JP6521553B1 (ja) | 2018-12-26 | 2018-12-26 | 置換金めっき液および置換金めっき方法 |
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Cited By (1)
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JP2022087472A (ja) * | 2020-12-01 | 2022-06-13 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | 非シアン系の置換金めっき液及び置換金めっき方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5754264A (ja) * | 1980-08-04 | 1982-03-31 | Schering Ag | |
US20050031895A1 (en) * | 2000-08-21 | 2005-02-10 | Kazuyuki Suda | Electroless displacement gold plating solution and additive for use in preparing plating solution |
JP2012046792A (ja) * | 2010-08-27 | 2012-03-08 | Electroplating Eng Of Japan Co | 置換金めっき液及び接合部の形成方法 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5754264A (ja) * | 1980-08-04 | 1982-03-31 | Schering Ag | |
US20050031895A1 (en) * | 2000-08-21 | 2005-02-10 | Kazuyuki Suda | Electroless displacement gold plating solution and additive for use in preparing plating solution |
JP2012046792A (ja) * | 2010-08-27 | 2012-03-08 | Electroplating Eng Of Japan Co | 置換金めっき液及び接合部の形成方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022087472A (ja) * | 2020-12-01 | 2022-06-13 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | 非シアン系の置換金めっき液及び置換金めっき方法 |
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