TWI284157B - Electroless gold plating solution - Google Patents
Electroless gold plating solution Download PDFInfo
- Publication number
- TWI284157B TWI284157B TW093109714A TW93109714A TWI284157B TW I284157 B TWI284157 B TW I284157B TW 093109714 A TW093109714 A TW 093109714A TW 93109714 A TW93109714 A TW 93109714A TW I284157 B TWI284157 B TW I284157B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- plating solution
- gold plating
- gold
- electroless gold
- Prior art date
Links
- 239000010931 gold Substances 0.000 title claims abstract description 58
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 58
- 238000007747 plating Methods 0.000 title claims abstract description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- -1 amine compound Chemical class 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 claims 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 125000000468 ketone group Chemical group 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 238000005476 soldering Methods 0.000 abstract description 4
- 229910003202 NH4 Inorganic materials 0.000 abstract description 3
- 125000002541 furyl group Chemical group 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 abstract description 2
- 125000004076 pyridyl group Chemical group 0.000 abstract description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000004471 Glycine Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 241000933336 Ziziphus rignonii Species 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002344 gold compounds Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000006519 CCH3 Chemical group 0.000 description 1
- 101100133719 Caenorhabditis elegans npr-18 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- VJOUUGUSJOHNRQ-UHFFFAOYSA-N OC[Na] Chemical compound OC[Na] VJOUUGUSJOHNRQ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- PDMYFWLNGXIKEP-UHFFFAOYSA-K gold(3+);trithiocyanate Chemical compound [Au+3].[S-]C#N.[S-]C#N.[S-]C#N PDMYFWLNGXIKEP-UHFFFAOYSA-K 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- CYFJIBWZIQDUSZ-UHFFFAOYSA-N thioglycine Chemical compound NCC(S)=O CYFJIBWZIQDUSZ-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemically Coating (AREA)
Description
1284157 玖、發明說明 【發明所屬之技術領域】 本發明有關電鍵技術,係關於無電解錢金液者。 【先前技術】 無電解鍍金係適用於印刷電路板之電路、IC(積體電路) 封裝、ITO(銦錫氧化物)基板、Ic卡等之電子工業零件之 端子或電路表面。 在基底為無電解鍍鎳被膜上進行厚度0 05至〇 之取代型無電解鍍金時,特別是在電鍍反應一開始時,鎳 與金之取代反應加速,選擇性強烈攻擊無電解鎳被膜上的 析出粒子之粒界部分,以致析出粒子進行深度侵蝕,並於 鍍金被膜下形成缺陷部分。依情況而定,缺陷部分有時會 連續生成,或集中生成,甚至引起鍍金被膜之外觀不佳(在 j面產生點蝕(pitting))。再者,所析出的金被膜之膜厚儘 管薄至0.1// m以下,惟被深度侵蝕,由於該種取代型鍍 金液所引起的無電解鍍鎳被膜之脆弱化及與鍵金被膜間的 抢接性不足,因此,在耐久性試驗時發生剝離,或在進行 焊接之時無法確保充分的焊接強度。如此,使用以往技術 之無電解鍍金液時,由於鍍金被膜表面存在點蝕,使得因 焊接強度的不足所引起的不良品之發生在球閘陣列 (BGA : Ball Grid Array)型半導體封裝等方面上而成為 題。 曰本專利特開2〇〇1_107259號公報中,揭示一種作為 取代型無電解鍍金液係含有次磷酸鹽或肼(hydraziM)、以 5 315705 1284157 及直鏈狀燒基胺者。此種取代型無電解鑛金液之目的係使 基底為錄面 如没減低,並防止因熱履程所引起的焊球等 焊接構件之固定綠择γ > 心5$度(抗拉強度·· shear strength)的低落。 曰本專利特開平6-280039號公報中,揭示含有水 六 a物錯合劑(comPlexing agent)、還原劑、以及 胺等含氮化合物之無電解電鍍浴中添加非離子性界面活性 d及/或非離子性聚合物之安定齊卜以冑可能之方式防止電 鍍擴散的電鍍液。 【發明内容】 本毛月之目的在於提供一種能製得表面無點蝕的鍍金 被膜,而在進行焊接時能確保充分的焊接強度之無電解鍍 金液。 為解決上述課題而專心研究的結果,發現經由使無電 解鍍金液中含有特定之羥基烷基磺酸或其鹽、及胺化合物 者,即可製得表面無點蝕的鍍金被膜,而完成本發明。亦 即,本發明係如下所述。 (1)一種無電解鍍金液,其特徵為:含有金之水溶性化合 物,並含有作為還原劑之下述通式所示之羥基烷基磺酸或 其鹽、及胺化合物。
HO-CH-teH^-SOeX
R (上述式中,R表示氫、羧基、或可具有取代基的苯基、萘 基、飽和或不飽和烧基、乙醯基' 丙酮基、吼續基、以及 315705 6 1284157 呋喃基之任一種,X表示氫、Na(鈉)、K(鉀)、以及NH4(銨) 之任一種,η為0至4之整數。) (2) 如上述(1)之無電解鍍金液,其中,再含有磷酸系化合 物。 (3) 如上述(1)或(2)之無電解鍍金液,其中,上述通式所示 之還原劑係羥基甲磺酸鈉(HOCH2S03Na)者。 (4) 如上述(1)至中任一項之無電解鍍金液,其中,上述 胺化合物係三乙四胺(H2N(CH2)2NH(CH2)2NH(CH2)2NH2) 者0 (5)—種鍍金物,其特徵為:使用上述(1)至(4)中任一項之 無電解鍍金液所製作者。 【實施方式】 以下,就本發明之無電解鍍金液,加以詳細說明。 本發明之鍍金液係作為金來源之金化合物,而祇要是 水溶性者則並不特別限定,惟其最大特徵係含有特定之羥 基烷基磺酸或其鹽、及胺化合物。 因此,本發明之鍍金液,係至少將水溶性金化合物、 及特定之羥基烷基磺酸或其鹽、以及胺化合物溶解於水系 溶劑中者,對溶劑而言,較佳為水。 對水溶性金化合物而言,較佳為氰化金、亞硫酸金、 T代硫酸金、硫氰酸金、氯金酸、或其鹽(例如鈉鹽、鉀鹽、 銨鹽等)。本發明之無電解鍍金液係鍍液中之此等金化合物 以含有金濃度為〇」至100g/公升者為佳,更佳者為含有 0·5至20g/公升。如金濃度在〇 lg/公升以下時,則金之取 315705 7 1284157 代速度明顯變慢,而即使在1 OOg/公升以上時,其效果仍 飽和而並無好處(merit)。 對還原劑而言,係使用下述通式所示之經基烧基石黃酸 或其鹽。
HO-CH-iCH^-SOgX
I
R (上述式中,R表示氫、羧基、或可具有取代基之苯基、萘 基、飽和或不飽和烧基、乙醯基、丙酮基、D比咬基、以及 呋喃基之任一種,X表示氫、Na、K以及NH4之任一種, η為0至4之整數。) 上述式中,作為R中之苯基、萘基、飽和或不飽和烷 基、乙醯基、丙酮基、吡啶基、以及呋喃基之取代基而言, 可例舉如· _素元素、烷氧基、硝基、羥基、磺酸基或其 鹽、苯基、乙醯基等。對_素元素而言,較佳為氣,對烷 氧基而言,較佳為低級烷氧基,例如曱氧基。又,對磺酸 基之鹽而言,可例舉如:鹼金屬鹽等,而較佳為鈉鹽。 對飽和或不飽和烷基而言,較佳為碳數丨至4之烷基。 又,上述式中,對χ而言,較佳為鈉。 對上述一般式所不之羥基烷基磺酸或其鹽之具體例而 口可例舉如下之化合物等,特別是NO· 1及Ν0.2之化合 物為適用。 315705 8 1284157 1 H0-CH2-S03Na 2 H0-CH2-CH2-S03Na H0-CH-S03Na 6 4 H0-CH-S03Na 5
Cl H0-CH-S03Na
6 H0-CH-S03Na
OCHs 1284157 7 H0-CH-S03Na ^^och3 8 H0-CH-S03Na
no2 9 (HO - CH - S03Na) · H20
HO-CH
I S03Na 10 H〇-CH-SOsNa
I CC13 11 H0-CH-S03Na
I CHC12 12 H0-CH-S03Na CH2C1 1284157 13 H0-CH-S03NaI CH(OH)2 14 H0-CH-S03Na C=0
I ch3 15 H0-CH-S03Na
I ch3 16 17 H0-CH-S03NaI c2h5 H0-CH-S03Na nPr 18 H0-CH-S03Na iPr m 19 H0-CH-S03NaI iBu 11 315705 201284157 HO-CH-SOaNaI CHII ch2 21 22 H0-CH-S03NaI COOH HO-CH-SOaNa II CH ch3 23 24 HO-CH-SOaNa CH2 I CH(OH) I SOaNa HO-CH-SOaNa CH2 I CH2 CH(OH) I SOaNa 12 315705 1284157 25
Η OH 〕C=C 二 CH
SOaNa S03Na 26
HO
S03Naώ /H C=C. OH
H CH S03Na 27
28 OH-CH-SOaNa
29 HO-CH-SOaNa /^^CH-S03Na 13 315705 301284157 31 H0-CH-S03Na
CH-S03Na I OH 32 HO-CH-SOsNa 0 33 H0-CH-S03Na
34
OH
CH-SOaNa 14 315705 1284157 35 36 37 HO-CH-SOaNa
I
C^CH H0-CH-S03Na
I CH2=C-CH3
NaOaS - CH - CH2CH2CH2 - CH - S03Na I I
OH OH 38
NaOsS - CH - CH2CH2CH2CH2- CH - S03Na OH OH H0-CH-S03Na
I
CH
II
CH έ H0-CH-S03Na
I CH2 (OH) HO-CH-SOaNa
I CH(OH) CH3 15 315705 1284157 42 H0-CH-S03Na
I CH(OH)
I CH2(〇H) 43 H〇-CH-S〇3Na
I CH(OH)
I CH(OH)
I CH(OH)
I S03Na 44 HO-CH-SOaNa
I
NaOaS - CH - CH2 - C - CH2- SOaNa I I
OH OH 45 HO-CH-SOsNa
I CH2
I c=o
I ch3 46 HO-CH-SOsNa
I c6h5-c-oh c6h5 上述羥基烷基磺酸或其鹽,較佳為在鍍液中含有o.l 至20g/公升,更佳為含有0.5至10g/公升,如含量為0.1 g/ 公升以下時,則金的析出速度變慢,又在20g/公升以上時, 16 315705 1284157 =由於發生浴分解(bath dec〇mp〇siti〇n)的可能性增高而 加匕合物而言,可例示如:二乙三胺、三乙四胺、 2五胺、五乙六胺等纟1分子中具有1級胺及2級胺之 ::物,甲胺、乙胺、丙胺、丁胺、戊胺、己胺等單胺化 :々,甲-胺、乙二胺、丙二胺、丁二胺、戊二胺、己二 胺專一胺化合物。 —又,再可例示如:與上述化合物鍵結苯環等芳香族環 之方香族胺、直接鍵結胺基之苯胺等芳香族胺化合物。又, 為改善對水的溶解性,因此,亦可使用與上述化合物鍵結 之經基、缓基或續酸基等極性高之取代基的化合物或形成 鹽酸鹽等鹽之化合物。 胺化合物,較佳為在鍍液中含有〇1至3〇g/公升,更 佳為含有0.5至20g/公升。如含量為〇lg/公升以下,則鎳 面將進行粒界侵蝕(intengranular c〇rr〇si〇n),而可能會引 起鍍金被膜外觀的不佳。又,如含量為3〇g/公升以上時, 則由於發生浴分解的可能性增高而不宜。 又,本發明之無電解鐘金液係可因應必要而添加填酸 系化合物之pH緩衝劑。 磷酸系化合物,可例舉如··磷酸、焦磷酸、或此等酸 之鹼金屬、鹼土類金屬、銨鹽、磷酸二氫鹼金屬、磷酸二 氫鹼土類金屬、磷酸二氫銨、磷酸氫二鹼金屬、磷酸氫二 鹼土類金屬、磷酸二氫銨等。鍍液中之磷酸系化合物之濃 度,較#為0.1至200g/公升,更佳為】至1〇〇g/公升。 17 315705 1284157 又,本發明之鍍金液中,可再含有胺基羧酸(aniino carboxylic acid)化合物之錯合劑,對胺基羧酸化合物而 言,可例舉如··乙二胺 N,N,N’,N’-tetra acetic acid)、經基乙基乙二胺三乙酸、二 經基乙基乙《«»^胺-—乙酸、丙烧二胺四乙酸、二乙三胺五乙 酉文、二乙四胺六乙酸、甘胺酸(glyCine)、甘胺醯甘胺酸、 甘胺醯甘胺醯甘胺酸、二羥乙基甘胺酸、胺基二乙酸、經 基乙基胺基二乙酸、胺三乙酸、胺三丙酸、或此等之鹼金 屬、鹼土類金屬、銨鹽等。鍍液中之胺基羧酸化合物之濃 度,較佳為0.1至200g/公升,更佳為1至1〇〇g/公升。如 胺基酸化合物之濃度在〇.lg/公升以下時,則作為錯合劑之 效果不彰,而即使在200g/公升以上時,其效果因飽和而 並無好處。 本發明之鍍金液中,為使金錯合物〇〇1111)1“)安定化、 並改善浴安定性起見,亦可添加氰化鉀或氰化鈉等之氰化 物。如氰化物之添加量過多時,則由於會腐蝕基底為鎳之 被膜以致容易產生點蝕,因此,較佳為在〇 〇1至公升 之範圍添加。 再者,作為反應促進劑而添加鉈(T1)化合物或鉛化合 物亦為有效。對此等化合物之添加量而言,以金屬計,較 ‘為0.01至50mg/公升。如反應促進劑之添加量過多時, 則會引起浴分解。 -本發明之鍍金液之pH,從金之析出速度、電鍍被膜之 外硯、以及浴安定性的觀點來看,較佳為按p Η 5至9使用, 315705 18 1284157 特佳為按pH 6至8使用。 為pH之調整,可使用氫氧化鉀、氫氧化鈉、氨等之 驗性化合物,硫酸、磷酸等之酸性化合物。 又,本發明之鍍金液,從浴安定性及金之析出速度的 觀點來看,較佳為按浴溫60至90°C使用。 如使用本發明之鍍金液以實施電鍍時,則將印刷電路 板等之被鏟材浸潰於浴中。被鍍材較佳為基底經實施鍍鎳 等之後之物,如使用本發明之鍍金液電鍍時,則所製得鍍 金被膜之表面並不會產生點蝕,與基底鍍鎳之被膜間的密 接性良好,實施焊接時可確保焊接強度。 (實施例) 就本發明之較佳實施形態,藉由下述的實施例及比較 例加以說明。 實施例1至2及比較例1 [ 2 造浴如表1所示的各組成之鍍金液。作為被鍍材係使 用鍍銅印刷電路板,並按下述方式實施至無電解鍍金步 驟’依表1所記載之條件實施無電解鍍金。 酸性脫脂步驟(日鑛金屬電鍍社製KG_512)45°C,5分鐘 —溫水沖洗50至60。(:,1分鐘 —水洗 —軟I虫刻(soft etching)(遇硫酸鈉80g/公升,硫酸 20ml/公升) —水洗 —酸沖洗〔硫酸30ml/公升) v 19 315705 1284157 4水洗 —活化劑(日鑛金屬電鍍社製KG_522)25。。,3分鐘 〜水洗 4酸浸潰(硫酸3Oml/公升) 水洗 〜無電解鍍鎳(曰鑛金屬電鍍社製KG_ 5 3 0)8 5 °C,3分鐘 水洗 無電解鍍金 就所製得電鍍被膜,按如下方式加以評價。使用SEM 在3000倍下觀察,以目視觀察有無點蝕存在。將實施例1 及比較例1至2之鍍金被膜之SEM照片,分別表示於第1 圖至第3圖。照片中,可以觀察到黑點之點蝕。實施例1 之鍍金被膜中並未觀察到黑點(亦即點蝕),而在比較例1 及2之鍍金被膜中,則發現有點蝕。又,實施例2之鍍金 被膜亦與實施例1同樣,並未觀察到點蝕。 另外’析出速度係在實施電鍍20分鐘後,使用精工電 子工業(股)製螢光X線膜厚計SFT-3200測定,以求出電鍍 膜厚。 評價結果如表1所示。 20 315705 1284157 表1 無電解鍍金液之組成及特性 實施例1 實施例2 比較例1 比較例2 點蝕 〇 〇 X Δ 析出速度(// m/20min) 0.12 0.10 0.081 0.055 氰化金鉀(g/L) 2 2 2 2 EDTA(g/L) 10 10 0 10 三乙四胺(g/L) 10 10 0 10 麟酸二氫鈉· 2水合物(g/L) 34 34 34 34 羥基甲磺酸鈉(g/L) 2 — 2 0 經基乙績酸鈉(g/L) 一 2 — — pH 7.0 7.0 7.0 7.0 浴溫度(°C) 88 88 88 88 pH係使用氫氧化鉀加以調整 其次,對實施例1及比較例1所製得之電鍍被膜,試 驗密合強度。 P接雄、合強度,係作為焊接球而使用
Pb(錯)/Sn(錫)= 37/63,0.4mm (/) (SPARKLE BALLS 千住金 屬製)’作為焊劑而使用RMA型(Nil-loo VK-1旭化學研 究所製)’依如下述實施加熱式可衝擊試驗(bumpable test)。試驗舉行12次,並去除其中的上下異常值,將最大 值、最小值、平均值表示於表2中。 測定機器:黏結劑試驗機4000系列(德伊奇社製)
加熱條件:設定溫度…270°C 加熱時間…5秒鐘 冷卻 OFF··· 50〇C 試驗速度…300 // m/秒鐘 315705 21 1284157 軟溶(reflow)爐:遠紅外線式迴焊裝置 (RF-330日本脈衝技術研究所製) 迴焊條件:峰值溫度…230。(: 表2 —-------- 例 ~ϊ Λ η η 最大值 1462 __ — — Γ_ 1181 T32l ----—--- 丄j / 7 --__ _U85_ 單位:gf 由表2之結果可知,實施例丨所得被膜之焊接密合強 度,係較在比較例1所得被膜之焊接密合強度為強。此原 因可能係由於實施例i之被膜中並無點蝕因而鎳對鍍金層 的擴散少,以致難於鎳表面形成含磷率為高之層,^者2 於無點蝕之故,鎳表面難以被氧化因而提升密合強度。 (產業上之利用可能性) 如抓用本發明之無電解鍍金液,則可製得表面無點蝕 的鍍金被膜。再者,如將本發明之無電解鍍金液適用於印 刷電路板之電路、IC封裝、IT〇基板、IC卡等之電子工業 零件=端子或電路表面,則可改善基底為無電解鍍錄被膜 間的密合性,並在實施焊接時可確保充分的焊接強度。 【圖式簡單說明】 第1圖係實施例1之鍍金被膜面之SEM(掃瞄式電子 顯微鏡)照片。 第2圖係比較例丨之鍍金被膜面之SEm照片。 ▲々3圖係比較例2之鍍金被膜面之SEM照片。 315705 22
Claims (1)
1284157 拾、申請專利範圍: 1. 一種無電解鐘金液,其特徵為:含有金之水溶性化合 物,並含有作為還原劑之下述通式所示之羥基烧基績酸 或其鹽,及胺化合物 H0 - CH - (CR2)n ~ s〇3X R (上述式中,R表示氫、羧基、或可具有取代基的苯基、 奈基、飽和或不飽和烷基、乙醯基、丙酮基、吼唆基、 乂及口夫喃基之任一種,X表示氫、Na、κ、以及nh4之 任一種,η為0至4之整數)。 2·如申請專利範圍第丨項之無電解鍍金液,其中,再含有 磷酸系化合物。 3·如申請專利範圍第1項之無電解鍍金液,其中,上述通 式所示之還原劑係羥基曱磺酸鈉(H〇CH2S〇3Na)者。 4·如申請專利範圍第丨項之無電解鍍金液,其中,上述胺 化合物係二乙四胺(H2N(CH2)2NH(CH2)2NH(CH2)2NH2) 者。 5· ~種鍍金物,其特徵為:使用申請專利範圍第i項至第 4項中任一項之無電解鍍金液所製作者。 315705 23
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KR (1) | KR100749992B1 (zh) |
CN (1) | CN100510174C (zh) |
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US7300501B2 (en) * | 2004-04-05 | 2007-11-27 | Nikko Materials Co., Ltd. | Electroless gold plating liquid |
JP5526459B2 (ja) * | 2006-12-06 | 2014-06-18 | 上村工業株式会社 | 無電解金めっき浴及び無電解金めっき方法 |
JP5526458B2 (ja) * | 2006-12-06 | 2014-06-18 | 上村工業株式会社 | 無電解金めっき浴及び無電解金めっき方法 |
JP4941650B2 (ja) * | 2007-01-11 | 2012-05-30 | 上村工業株式会社 | 無電解金めっき浴のめっき能維持管理方法 |
JP5013077B2 (ja) | 2007-04-16 | 2012-08-29 | 上村工業株式会社 | 無電解金めっき方法及び電子部品 |
JP4831710B1 (ja) | 2010-07-20 | 2011-12-07 | 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 | 無電解金めっき液及び無電解金めっき方法 |
JP6619563B2 (ja) * | 2015-04-30 | 2019-12-11 | 日本高純度化学株式会社 | 無電解金めっき液、アルデヒド−アミン付加体補給液及びそれらを用いて形成した金皮膜 |
CN105543816A (zh) * | 2016-02-01 | 2016-05-04 | 哈尔滨工业大学(威海) | 一种化学镀金液 |
JP6329589B2 (ja) | 2016-06-13 | 2018-05-23 | 上村工業株式会社 | 皮膜形成方法 |
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JP3920462B2 (ja) * | 1998-07-13 | 2007-05-30 | 株式会社大和化成研究所 | 貴金属を化学的還元析出によって得るための水溶液 |
US6383269B1 (en) * | 1999-01-27 | 2002-05-07 | Shipley Company, L.L.C. | Electroless gold plating solution and process |
JP4932094B2 (ja) * | 2001-07-02 | 2012-05-16 | 日本リーロナール有限会社 | 無電解金めっき液および無電解金めっき方法 |
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JPWO2004111287A1 (ja) | 2006-07-20 |
TW200500496A (en) | 2005-01-01 |
CN100510174C (zh) | 2009-07-08 |
KR20060031617A (ko) | 2006-04-12 |
CN1802452A (zh) | 2006-07-12 |
WO2004111287A2 (ja) | 2004-12-23 |
HK1090096A1 (en) | 2006-12-15 |
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