CN113737159A - Pre-immersion liquid for inhibiting copper surface chemical plating and diffusion plating and preparation method and application thereof - Google Patents
Pre-immersion liquid for inhibiting copper surface chemical plating and diffusion plating and preparation method and application thereof Download PDFInfo
- Publication number
- CN113737159A CN113737159A CN202111004311.1A CN202111004311A CN113737159A CN 113737159 A CN113737159 A CN 113737159A CN 202111004311 A CN202111004311 A CN 202111004311A CN 113737159 A CN113737159 A CN 113737159A
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- Prior art keywords
- plating
- acid
- copper
- liter
- comprises water
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- 238000007747 plating Methods 0.000 title claims abstract description 100
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- 238000009792 diffusion process Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 31
- 238000007654 immersion Methods 0.000 title claims abstract description 27
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 aliphatic nitrogen-containing carboxylic acid compounds Chemical class 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 52
- 230000000996 additive effect Effects 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 238000007598 dipping method Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000012445 acidic reagent Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 26
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 24
- 229910052737 gold Inorganic materials 0.000 claims description 21
- 239000010931 gold Substances 0.000 claims description 21
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- AMSDWLOANMAILF-UHFFFAOYSA-N 2-imidazol-1-ylethanol Chemical compound OCCN1C=CN=C1 AMSDWLOANMAILF-UHFFFAOYSA-N 0.000 claims description 16
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 15
- 229960004308 acetylcysteine Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 12
- IICHYVITRCPMBX-UHFFFAOYSA-N c1cc[nH+]cc1.CCC(O)S([O-])(=O)=O Chemical compound c1cc[nH+]cc1.CCC(O)S([O-])(=O)=O IICHYVITRCPMBX-UHFFFAOYSA-N 0.000 claims description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- RILPVBCCHVYIJF-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCN1CN(C)C=C1 RILPVBCCHVYIJF-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004201 L-cysteine Substances 0.000 claims description 7
- 235000013878 L-cysteine Nutrition 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- WHNXAQZPEBNFBC-UHFFFAOYSA-K trisodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O WHNXAQZPEBNFBC-UHFFFAOYSA-K 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 235000001014 amino acid Nutrition 0.000 claims description 6
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940103494 thiosalicylic acid Drugs 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- WLVHZZYNSMMNGK-UHFFFAOYSA-N [Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO Chemical compound [Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO WLVHZZYNSMMNGK-UHFFFAOYSA-N 0.000 claims description 2
- BTKOPDXMVKYSNL-UHFFFAOYSA-N [Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O Chemical compound [Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BTKOPDXMVKYSNL-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 claims 6
- TZBXHAADXXYJPG-UHFFFAOYSA-N N1=CC=CC=C1.C(CC)S(=O)(=O)OO Chemical compound N1=CC=CC=C1.C(CC)S(=O)(=O)OO TZBXHAADXXYJPG-UHFFFAOYSA-N 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001431 copper ion Inorganic materials 0.000 abstract description 16
- 230000004913 activation Effects 0.000 abstract description 14
- 238000007323 disproportionation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 3
- 238000000576 coating method Methods 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008213 purified water Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 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 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- IVYPWZOOVZGKCT-UHFFFAOYSA-N [Na].[Na].[Na].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O Chemical compound [Na].[Na].[Na].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O IVYPWZOOVZGKCT-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
-
- 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
Abstract
The invention relates to a pre-immersion liquid for inhibiting chemical plating and diffusion plating of a copper surface, and a preparation method and application thereof. Each liter of the prepreg comprises water, 5g to 100g of acid reagent and 0.05g to 5g of prepreg additive; the acid reagent is sulfuric acid and/or hydrochloric acid; the pre-dipping additive is at least one of nitrogen-containing aromatic heterocyclic compounds, aliphatic nitrogen-containing carboxylic acid compounds, sulfur-containing fatty acid compounds and organic amine compounds. This pre-dip can shield and apply the monovalent copper ion at plating surface edge to prevent that monovalent copper ion from taking place disproportionation reaction and growing out copper simple substance at plating surface edge and substrate position, and then reduce the diffusion coating problem that palladium ion leads to at plating surface edge and substrate position and the replacement reaction of copper in the activation liquid, or because of the diffusion coating problem that nickel bath activity leads to too strong, finally play the reduction and lead to the problem that the circuit board yields descends because of the diffusion coating problem, have extensive application prospect.
Description
Technical Field
The invention relates to the field of magnetic functional materials, in particular to a pre-immersion liquid for inhibiting chemical plating and diffusion plating of a copper surface, and a preparation method and application thereof.
Background
In the production process of Printed Circuit Boards (PCBs), electroless nickel-gold (or nickel-plating) and nickel-palladium-gold (nickel-palladium-gold) are two common final surface treatment methods for metal wiring on a Circuit Board. Electroless nickel-gold is formed by chemically plating a layer of nickel on the surface of copper, and then plating a layer of gold on the surface of nickel by a displacement reaction. The processing method enables the circuit board to have multiple functions of welding, contact conduction, routing, heat dissipation and the like.
The activation of the metallic copper surface on the circuit board is required prior to electroless nickel plating because the copper surface does not spontaneously drive the reduction of nickel ions to effect electroless nickel deposition. In industry, palladium activating solution is usually used to contact with circuit board, and electrons released after dissolving copper surface in trace amount are used to reduce palladium ions into metal palladium, so as to form a thin palladium layer on the copper surface as a catalytic catalyst for nickel deposition, thereby generating electroless deposition of nickel. However, this electroless nickel plating process typically results in palladium metal being deposited not only on the copper surface but also on other non-plated surfaces of the circuit board (e.g., solder resist inks, dry films, or bare circuit board substrates), resulting in subsequent nickel deposition not only on the copper lines, but also on the board surfaces in the vicinity of the copper lines, a phenomenon known as "strike-through". Slightly, the gold deposit is formed in a dot shape on the surface of the circuit board, which results in a thick copper surface in the case of severe cases, and in a bridge short between wiring and contact pads in the case of severe cases, and particularly, in a high-density circuit having a line width and a line pitch of about 75 μm or less, the short-circuit phenomenon is more likely to occur.
In order to avoid the above phenomenon, the industry generally adds a post-dipping step between the steps of treating the circuit board with the palladium activating solution and dissolving nickel, so as to remove the excessive palladium ions adsorbed on the non-plating surface. Currently known methods of improvement are: (1) adding an inhibitor into the activation tank to reduce the adsorption of palladium on a non-plating position; (2) the cleaning effect is enhanced by optimizing the post-soaking formula.
At present, no relevant report that the nickel-gold or nickel-palladium-gold infiltration is avoided by improving the formula of the pre-immersion liquid is seen, the traditional pre-immersion liquid is only used for maintaining the acidity of the activation liquid and enabling the copper surface to enter the activation cylinder in an oxide-free state, the commonly used pre-immersion liquid is generally a low-concentration aqueous solution of sulfuric acid or hydrochloric acid, and the infiltration avoiding effect is almost not achieved.
However, after the copper surface is microetched, the copper surface is bitten to release monovalent and divalent copper ions, the monovalent copper ions may generate a disproportionation reaction to generate divalent copper ions and a copper simple substance, if the copper surface is microetched, the copper simple substance produced by the disproportionation reaction cannot be removed through presoaking, and is continuously adsorbed at the edge position or the base material position, and after passing through the activation tank, palladium and the simple substance copper generate a displacement reaction and is further adsorbed at the edge of the copper surface or the base material position, so that the thin circuit board is easy to be subjected to diffusion plating. In order to enhance the effect of preventing nickel-gold/nickel-palladium-gold penetration, the industry needs to find a suitable pre-immersion liquid for improving the copper surface chemical plating urgently.
Disclosure of Invention
Based on the above, the invention provides the pre-immersion liquid which can effectively inhibit the chemical plating and diffusion plating of the copper surface.
The technical scheme of the invention is as follows:
a pre-immersion liquid for inhibiting chemical plating and diffusion plating of a copper surface, wherein each liter of the pre-immersion liquid comprises water, 5g to 100g of an acidic reagent and 0.05g to 5g of a pre-immersion additive;
the acid reagent is sulfuric acid and/or hydrochloric acid;
the pre-dipping additive is at least one of nitrogen-containing aromatic heterocyclic compounds, aliphatic nitrogen-containing carboxylic acid compounds, sulfur-containing fatty acid compounds and organic amine compounds.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of an acidic agent, and 0.05g to 3g of a prepreg additive.
In one embodiment, the pre-soak additive is a mixture of nitrogen-containing aromatic heterocycles and aliphatic nitrogen-containing carboxylic acids.
In one embodiment, the pre-soak additive is an organic amine compound.
In one embodiment, the pre-soak additive is a mixture of nitrogen-containing aromatic heterocyclic compounds and organic amine compounds.
In one embodiment, the pre-soak additive is a mixture of aliphatic nitrogen-containing carboxylic acid compounds and organic amine compounds.
In one embodiment, the nitrogen-containing aromatic heterocyclic compound is selected from at least one of pyridine, pyridinium hydroxypropanesulfonate, imidazole, 1- (2-hydroxyethyl) imidazole, 1-ethyl-3-methylimidazole methanesulfonate, quinoline, pyrimidine and triazole; and/or
The aliphatic nitrogenous carboxylic acid compound is selected from at least one of trisodium N-hydroxyethyl ethylenediamine triacetic acid, trisodium ethylenediamine tetraacetic acid and amino acid compounds; and/or
The sulfur-containing fatty acid compound is at least one selected from thioglycolic acid, sodium dimethyldithiocarbamate, thioglycolic acid, thiosalicylic acid, 2-mercaptoethanol, methionine, 3-mercaptopropionic acid and 2-mercaptobenzothiazole; and/or
The organic amine compound is at least one of aliphatic amine, alcohol amine and aromatic amine compounds.
In one embodiment, the amino acid compound is at least one selected from glycine, alanine, glutamic acid, L-cysteine and acetylcysteine; and/or
The aliphatic amine compound is at least one selected from polyethyleneimine, diethylenetriamine, 1, 4-butanediamine, diethylamine and triethylamine; and/or
The alcohol amine compound is at least one of triethanolamine and N-N dimethylethanolamine; and/or
The aromatic amine compound is at least one selected from aniline, o-toluidine and N-methylaniline.
In one embodiment, the pre-soak additive is a mixture of 1- (2-hydroxyethyl) imidazole and acetylcysteine.
In one embodiment, the pre-preg additive is a polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of 1-ethyl-3-methylimidazole mesylate and L-cysteine.
In one embodiment, the pre-soak additive is a mixture of pyridinium hydroxypropanesulfonate and acetylcysteine.
In one embodiment, the pre-preg additive is a mixture of ethylenediaminetetraacetic acid trisodium salt and polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of pyridinium hydroxypropanesulfonate and diethylenetriamine.
In one embodiment, the pre-preg additive is a mixture of trisodium N-hydroxyethylethylenediamine triacetate and polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of 1- (2-hydroxyethyl) imidazole and 1, 4-butanediamine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, 0.5g to 1g of 1- (2-hydroxyethyl) imidazole, and 0.5g to 1g of acetylcysteine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, and 0.5g to 1g of trisodium N-hydroxyethylethylenediaminetriacetic acid.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, and 0.05g to 0.5g of polyethyleneimine.
In one embodiment, each liter of the prepreg solution comprises water, 20g to 50g of hydrochloric acid, and 0.5g to 1g of glycine.
In one embodiment, each liter of the prepreg comprises water, 20g to 50g of hydrochloric acid, and 1g to 5g of 1, 4-butanediamine.
In one embodiment, each liter of the prepreg solution comprises water, 10g to 20g of sulfuric acid, 0.5g to 1g of 1-ethyl-3-methylimidazole methanesulfonate, and 0.05g to 0.5g of L-cysteine.
In one embodiment, each liter of the prepreg solution comprises water, 50g to 100g of sulfuric acid, 0.5g to 1g of pyridinium hydroxypropanesulfonate, and 0.5g to 1g of acetylcysteine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 10g of hydrochloric acid, and 1g to 2g of 3-mercaptopropionic acid.
In one embodiment, each liter of the prepreg liquid comprises water, 5g to 20g of sulfuric acid, 0.5g to 1g of ethylene diamine tetraacetic acid trisodium salt, and 0.5g to 1g of polyethyleneimine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 0.5g to 1g of pyridinium hydroxypropanesulfonate, and 1g to 2g of diethylenetriamine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 1g to 2g of trisodium N-hydroxyethylethylenediamine triacetate, and 0.5g to 1g of polyethyleneimine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of sulfuric acid, 1g to 2g of 1- (2-hydroxyethyl) imidazole, and 0.5g to 1g of 1, 4-butanediamine.
The invention also provides a preparation method of the pre-immersion liquid for inhibiting the chemical plating and diffusion plating of the copper surface, which comprises the following steps:
mixing said water, said acidic agent and said pre-soak additive.
The invention also provides the application of the pre-immersion liquid for inhibiting the chemical plating and diffusion plating of the copper surface in the chemical nickel plating.
The invention also provides a method for chemically plating nickel on the copper surface, which comprises the following steps:
soaking the base material with copper on the surface in the pre-dipping solution for inhibiting the chemical plating and diffusion plating of the copper surface to perform pre-dipping treatment;
and (4) activating and chemically plating nickel on the base material after the pre-soaking treatment.
In one embodiment, the surface copper-containing substrate is a PCB; the line width of the copper wire on the PCB circuit board and the line distance of the adjacent copper wire are both 60-120 mu m.
In one embodiment, the time for the pre-soaking treatment is 1min to 5 min; and/or
After the step of electroless nickel plating, the method also comprises the step of performing electroless gold plating on the surface of the nickel.
The invention has the following beneficial effects:
the pre-immersion liquid provided by the invention can shield monovalent copper ions at the edge of the plating surface, so that the monovalent copper ions are prevented from generating a copper simple substance on the edge of the plating surface and the position of a base material due to disproportionation reaction, the problem of diffusion plating caused by the replacement reaction of palladium ions in the activation liquid with copper at the edge of the plating surface and the position of the base material or the problem of diffusion plating caused by too strong activity of a nickel tank is further reduced, and the problem of reduction of the yield of a circuit board caused by the problem of diffusion plating is finally solved.
In addition, the pre-immersion liquid has low cost, and the preparation method and the application method are very simple, can meet the technical requirements of the industry, and have wide application prospects.
Drawings
FIG. 1 is a line width and line spacing diagram of copper surface before processing, the line width is about 80.28 μm;
FIG. 2 is a line width versus line spacing plot of electroless nickel gold without the use of a prepreg additive (comparative example 1), with a line width of about 47.57 μm;
fig. 3 is a line width versus line distance plot of electroless nickel gold plating with about 78.79 μm line width after the use of the prepreg additive (example 3).
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
In the present invention, "at least one" means any one, any two or more of the listed items.
The raw materials, reagents, and the like used in the following embodiments are all commercially available products unless otherwise specified.
The technical scheme of the invention is as follows:
a pre-immersion liquid for inhibiting chemical plating and diffusion plating of a copper surface, wherein each liter of the pre-immersion liquid comprises water, 5g to 100g of an acidic reagent and 0.05g to 5g of a pre-immersion additive;
the acid reagent is sulfuric acid and/or hydrochloric acid;
the pre-dipping additive is at least one of nitrogen-containing aromatic heterocyclic compounds, aliphatic nitrogen-containing carboxylic acid compounds, aliphatic sulfur-containing fatty acid compounds and organic amine compounds.
By adjusting the ratio of the acid to the prepreg additive, monovalent copper ions at the edge of the plated surface can be further shielded. In one preferred embodiment, each liter of the prepreg solution comprises water, 5g to 60g of the acidic reagent, and 0.05g to 3g of the prepreg additive. Further, the acidic reagent is sulfuric acid or hydrochloric acid.
In one embodiment, the pre-soak additive is a mixture of nitrogen-containing aromatic heterocycles and aliphatic nitrogen-containing carboxylic acids. The pre-dipping additive can better shield univalent copper ions at the edge of the copper surface generated by the microetching of the copper surface, prevent the univalent copper ions from generating a copper simple substance at the edge of a plating surface and the position of a base material through a disproportionation reaction, and further reduce the phenomenon of diffusion plating.
In one embodiment, the pre-soak additive is an organic amine compound. The pre-dipping additive can better shield univalent copper ions at the edge of the copper surface generated by the microetching of the copper surface, prevent the univalent copper ions from generating a copper simple substance at the edge of a plating surface and the position of a base material through a disproportionation reaction, and further reduce the phenomenon of diffusion plating.
In one embodiment, the pre-soak additive is a mixture of nitrogen-containing aromatic heterocyclic compounds and organic amine compounds. The pre-dipping additive can better shield univalent copper ions at the edge of the copper surface generated by the microetching of the copper surface, prevent the univalent copper ions from generating a copper simple substance at the edge of a plating surface and the position of a base material through a disproportionation reaction, and further reduce the phenomenon of diffusion plating.
In one embodiment, the pre-soak additive is a mixture of aliphatic nitrogen-containing carboxylic acid compounds and organic amine compounds. The pre-dipping additive can better shield univalent copper ions at the edge of the copper surface generated by the microetching of the copper surface, prevent the univalent copper ions from generating a copper simple substance at the edge of a plating surface and the position of a base material through a disproportionation reaction, and further reduce the phenomenon of diffusion plating.
In one embodiment, the nitrogen-containing aromatic heterocyclic compound is selected from at least one of pyridine, pyridinium hydroxypropanesulfonate, imidazole, 1- (2-hydroxyethyl) imidazole, 1-ethyl-3-methylimidazole methanesulfonate, quinoline, pyrimidine and triazole.
In one embodiment, the aliphatic nitrogen-containing carboxylic acid compound is at least one selected from trisodium N-hydroxyethylethylenediamine triacetate, trisodium ethylenediamine tetraacetate salt and amino acid compounds.
In one embodiment, the amino acid compound is at least one selected from the group consisting of glycine, alanine, glutamic acid, L-cysteine, and acetylcysteine.
In one embodiment, the sulfur-containing fatty acid compound is at least one selected from thioglycolic acid, sodium dimethyldithiocarbamate, thioglycolic acid, thiosalicylic acid, 2-mercaptoethanol, methionine, 3-mercaptopropionic acid and 2-mercaptobenzothiazole.
In one embodiment, the organic amine compound is at least one selected from the group consisting of aliphatic amines, alcohol amines, and aromatic amines.
In one embodiment, the aliphatic amine compound is at least one selected from the group consisting of polyethyleneimine, diethylenetriamine, 1, 4-butanediamine, diethylamine and triethylamine.
In one embodiment, the alcohol amine compound is selected from at least one of triethanolamine and N-N dimethylethanolamine.
In one embodiment, the aromatic amine compound is at least one selected from aniline, o-toluidine and N-methylaniline.
In one embodiment, the pre-soak additive is a mixture of 1- (2-hydroxyethyl) imidazole and acetylcysteine.
In one embodiment, the pre-preg additive is a polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of 1-ethyl-3-methylimidazole mesylate and L-cysteine.
In one embodiment, the pre-soak additive is a mixture of pyridinium hydroxypropanesulfonate and acetylcysteine.
In one embodiment, the pre-preg additive is a mixture of ethylenediaminetetraacetic acid trisodium salt and polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of pyridinium hydroxypropanesulfonate and diethylenetriamine.
In one embodiment, the pre-preg additive is a mixture of trisodium N-hydroxyethylethylenediamine triacetate and polyethyleneimine.
In one embodiment, the pre-soak additive is a mixture of 1- (2-hydroxyethyl) imidazole and 1, 4-butanediamine.
In one embodiment, the pre-soak additive is a mixture of 1- (2-hydroxyethyl) imidazole and 1, 4-butanediamine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, 0.5g to 1g of 1- (2-hydroxyethyl) imidazole, and 0.5g to 1g of acetylcysteine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, and 0.5g to 1g of trisodium N-hydroxyethylethylenediaminetriacetic acid.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 60g of sulfuric acid, and 0.05g to 0.5g of polyethyleneimine.
In one embodiment, each liter of the prepreg solution comprises water, 20g to 50g of hydrochloric acid, and 0.5g to 1g of glycine.
In one embodiment, each liter of the prepreg comprises water, 20g to 50g of hydrochloric acid, and 1g to 5g of 1, 4-butanediamine.
In one embodiment, each liter of the prepreg solution comprises water, 10g to 20g of sulfuric acid, 0.5g to 1g of 1-ethyl-3-methylimidazole methanesulfonate, and 0.05g to 0.5g of L-cysteine.
In one embodiment, each liter of the prepreg solution comprises water, 50g to 100g of sulfuric acid, 0.5g to 1g of pyridinium hydroxypropanesulfonate, and 0.5g to 1g of acetylcysteine.
In one embodiment, each liter of the prepreg solution comprises water, 5g to 10g of hydrochloric acid, and 1g to 2g of 3-mercaptopropionic acid.
In one embodiment, each liter of the prepreg liquid comprises water, 5g to 20g of sulfuric acid, 0.5g to 1g of ethylene diamine tetraacetic acid trisodium salt, and 0.5g to 1g of polyethyleneimine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 0.5g to 1g of pyridinium hydroxypropanesulfonate, and 1g to 2g of diethylenetriamine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 1g to 2g of trisodium N-hydroxyethylethylenediamine triacetate, and 0.5g to 1g of polyethyleneimine.
In one embodiment, each liter of the prepreg comprises water, 10g to 20g of sulfuric acid, 1g to 2g of 1- (2-hydroxyethyl) imidazole, and 0.5g to 1g of 1, 4-butanediamine.
The invention also provides a preparation method of the pre-immersion liquid for inhibiting the chemical plating and diffusion plating of the copper surface, which comprises the following steps:
mixing said water, said acidic agent and said pre-soak additive.
The invention also provides the application of the pre-immersion liquid for inhibiting the chemical plating and diffusion plating of the copper surface in the chemical nickel plating.
In one preferred embodiment, the preparation method of the pre-dip solution for inhibiting the electroless plating and diffusion of the copper surface comprises the following steps:
adding 1/2 volume of water (such as purified water), adding concentrated sulfuric acid or concentrated hydrochloric acid to obtain acid solution, adding prepreg additive, and adding water to desired volume to obtain desired prepreg.
The invention also provides a method for chemically plating nickel on the copper surface, which comprises the following steps:
soaking the base material with copper on the surface in the pre-dipping solution for inhibiting the chemical plating and diffusion plating of the copper surface to perform pre-dipping treatment;
and (4) activating and chemically plating nickel on the base material after the pre-soaking treatment.
In one embodiment, the time for the pre-soaking is 1min to 5 min.
In one embodiment, after the step of electroless nickel plating, the method further comprises the step of electroless gold plating on the surface of the nickel.
In one embodiment, the substrate with copper on the surface is a PCB circuit board.
In one embodiment, the line width of the copper wire on the PCB circuit board and the line distance between adjacent copper wires are both 60-120 μm.
In the art, the general procedure for electroless plating nickel gold on a microetched copper-containing circuit substrate (or PCB) is as follows:
copper circuit substrate → activation → cleaning → electroless nickel plating → electroless gold plating
A water washing step can be added between every two steps.
The invention creatively performs the pre-dipping treatment on the copper circuit substrate before the activation, and simultaneously, in order to avoid the judgment that the cleaning reagent influences the test effect, the cleaning is performed by adopting water (such as purified water) after the activation, and the test steps of the invention are as follows:
copper circuit substrate → presoaking → activating → washing → electroless nickel plating → electroless gold plating
A pre-dipping step: the prepared pre-dipping liquid is placed in front of the activation tank at normal temperature, and is added into the pre-dipping tank when in use, and the dipping time of the copper circuit substrate in the pre-dipping tank is about 1-5 min.
An activation step: the activating solution is palladium ion activating solution commonly used in the industry, the palladium activating time is about 1 minute, and the temperature of the activating step is room temperature.
And (3) water washing: the palladium in the non-plating area is removed by using purified water under the condition of room temperature.
Chemical nickel plating step: the nickel bath may be an electroless nickel bath commonly used in the industry, and the bath used herein is a 5183 series nickel bath (commercially available, available from Guangdong technologies, Inc.), operating at 80 deg.C, pH 4.3, and time 20 minutes.
Chemical gold plating: the gold bath may also be an electroless gold bath commonly used in the art, and the bath used herein is a 5186 series gold bath (commercially available, available from Guangdong technologies, Inc.) operating at 82 deg.C, pH 4.4, and time 6 minutes.
The following is a further description with reference to specific examples and comparative examples.
Example 1
The embodiment provides a pre-dipping solution for inhibiting the chemical plating and diffusion plating of a copper surface and a preparation method thereof.
1. The total volume of the pre-immersion liquid in this example was 1L, and the composition included water, 98% (mass ratio) concentrated sulfuric acid 50g, 1- (2-hydroxyethyl) imidazole 0.5g, and acetylcysteine 0.5 g.
2. The preparation method of the pre-immersion liquid in the embodiment is as follows:
to the reaction vessel was added 0.5L of purified water, 50g of 98% concentrated sulfuric acid was added to the purified water, then to the acid solution was added 0.5g of 1- (2-hydroxyethyl) imidazole and 0.5g of acetylcysteine, and finally purified water was added to 1L.
The formulations of the pre-dip solutions of examples 2 to 12 and comparative examples 1 to 5 are shown in table 1, the volumes of the pre-dip solutions are all 1L, purified water (raw material 1) is contained, and the preparation methods are the same as those of example 1 except that the kinds of the corresponding raw materials are replaced with the raw materials shown in table 1. The pre-dip solutions prepared in each of the examples and comparative examples were prepared for use in a pre-dip tank before activation.
TABLE 1
The application test part:
preparing 18 FR-4 epoxy resin/glass fiber hard boards containing copper wires and subjected to conventional microetching, wherein the sizes of the hard boards are 10cm multiplied by 10cm, and the line width and the line distance on the substrate are 80-90 mu m. The substrates are prepared by the steps of pre-dipping, activating, cleaning, electroless nickel plating and electroless gold plating, and metal nickel and gold are deposited on the substrates in sequence through the processes of pre-dipping, activating, cleaning, electroless nickel plating and electroless gold plating, so as to serve as application examples 1-12 and application comparative examples 1-6, wherein the pre-dipping steps are respectively performed for 5min by using the pre-dipping solutions prepared in the above examples 1-12 and comparative examples 1-6.
The microetching copper-containing circuit board is presoaked according to the method of the invention, then activation, water washing, chemical nickel plating and chemical gold plating are carried out, and the nickel-gold diffusion plating condition of the copper circuit is observed on the processed substrate under a metallographic microscope.
And observing the nickel-gold diffusion plating condition of the copper circuits of all the substrates subjected to nickel-gold melting by adopting a metallographic microscope. In the test, the ratio of the line spacing after nickel-gold melting to the original line spacing is used to represent the diffusion plating condition of the copper circuit, and the larger the numerical value is, the smaller the line spacing change is, the more slight the diffusion plating condition is, otherwise, the more serious the diffusion plating condition is. The results of the plating test are shown in Table 2.
TABLE 2
As can be seen from table 2, when the substrate was pre-dipped in the pre-dip solutions prepared in examples 1 to 12 of the present invention and electroless nickel-gold plating was performed, the pitch was 70% or more of the original pitch, and when the pre-dip solution of example 3 was used for the pre-dipping, the final pitch could even reach 98% of the original pitch. And after the substrates are presoaked by the presoaking solutions of comparative examples 1 to 6 which are not in the scope of the present invention and are chemically plated with nickel and gold, the wire pitch is only 59.3 to 65 percent of the original wire pitch. Therefore, the pre-immersion liquid can effectively prevent the adsorption of redundant palladium in a non-plating area and can effectively prevent the phenomenon of 'diffusion plating' of bridging between a copper wire and a copper surface.
FIG. 1 is a line-to-line spacing plot of the copper surface line width before processing, the line width being about 80.28 μm.
FIG. 2 is a line width and pitch graph of the substrate pre-dipped in the pre-dip (sulfuric acid solution only) of comparative example 1 and then electroless nickel-gold plated, with a line width of about 47.57 μm, which is 59.3% of the original line pitch.
FIG. 3 is a line width and pitch plot of the substrate pre-dipped with the pre-dip of example 3 (containing sulfuric acid and polyethyleneimine pre-dip additive) and then electroless nickel and gold plating, with a line width of about 78.79 μm, accounting for 98.1% of the original line pitch.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. A pre-immersion liquid for inhibiting chemical plating and diffusion plating of a copper surface is characterized in that each liter of the pre-immersion liquid comprises water, 5g to 100g of an acid reagent and 0.05g to 5g of a pre-immersion additive;
the acid reagent is sulfuric acid and/or hydrochloric acid;
the pre-dipping additive is at least one of nitrogen-containing aromatic heterocyclic compounds, aliphatic nitrogen-containing carboxylic acid compounds, sulfur-containing fatty acid compounds and organic amine compounds.
2. The pre-dip for inhibiting electroless copper plating bleeding according to claim 1, wherein each liter of the pre-dip comprises water, 5 to 60g of the acidic agent, and 0.05 to 3g of the pre-dip additive.
3. The pre-dip solution for inhibiting electroless copper plating bleeding according to claim 1, wherein the pre-dip additive is a mixture of nitrogen-containing aromatic heterocyclic compounds and aliphatic nitrogen-containing carboxylic acids; or
The pre-dipping additive is an organic amine compound; or
The pre-dipping additive is a mixture of nitrogen-containing aromatic heterocyclic compounds and organic amine compounds; or
The pre-dipping additive is a mixture of aliphatic nitrogenous carboxylic acid compounds and organic amine compounds.
4. The pre-dip solution for inhibiting copper surface electroless plating bleeding according to any one of claims 1 to 3, wherein the nitrogen-containing aromatic heterocyclic compound is at least one selected from pyridine, pyridinium hydroxypropanesulfonate, imidazole, 1- (2-hydroxyethyl) imidazole, 1-ethyl-3-methylimidazole methanesulfonate, quinoline, pyrimidine and triazole; and/or
The aliphatic nitrogenous carboxylic acid compound is selected from at least one of trisodium N-hydroxyethyl ethylenediamine triacetic acid, trisodium ethylenediamine tetraacetic acid and amino acid compounds; and/or
The sulfur-containing fatty acid compound is at least one selected from thioglycolic acid, sodium dimethyldithiocarbamate, thioglycolic acid, thiosalicylic acid, 2-mercaptoethanol, methionine, 3-mercaptopropionic acid and 2-mercaptobenzothiazole; and/or
The organic amine compound is at least one of aliphatic amine, alcohol amine and aromatic amine compounds.
5. The pre-dip for suppressing electroless plating and bleeding of a copper surface according to claim 4, wherein said amino acid compound is at least one selected from the group consisting of glycine, alanine, glutamic acid, L-cysteine and acetylcysteine; and/or
The aliphatic amine compound is at least one selected from polyethyleneimine, diethylenetriamine, 1, 4-butanediamine, diethylamine and triethylamine; and/or
The alcohol amine compound is at least one of triethanolamine and N-N dimethylethanolamine; and/or
The aromatic amine compound is at least one selected from aniline, o-toluidine and N-methylaniline.
6. The pre-dip for inhibiting electroless copper plating bleeding according to claim 1, wherein each liter of the pre-dip comprises water, 5 to 60g of sulfuric acid, 0.5 to 1g of 1- (2-hydroxyethyl) imidazole, and 0.5 to 1g of acetylcysteine; or
Each liter of the prepreg comprises water, 5g to 60g of sulfuric acid and 0.5g to 1g of trisodium N-hydroxyethyl ethylenediamine triacetate; or
Each liter of the prepreg comprises water, 5g to 60g of sulfuric acid and 0.05g to 0.5g of polyethyleneimine; or
Each liter of the prepreg comprises water, 20g to 50g of hydrochloric acid and 0.5g to 1g of glycine; or
Each liter of the prepreg comprises water, 20g to 50g of hydrochloric acid and 1g to 5g of 1, 4-butanediamine; or
Each liter of the prepreg comprises water, 10g to 20g of sulfuric acid, 0.5g to 1g of 1-ethyl-3-methylimidazole methanesulfonate, and 0.05g to 0.5g of L-cysteine; or
Each liter of the prepreg comprises water, 50g to 100g of sulfuric acid, 0.5g to 1g of pyridinium hydroxy propane sulfonate and 0.5g to 1g of acetylcysteine; or
Each liter of the prepreg comprises water, 5g to 10g of hydrochloric acid and 1g to 2g of 3-mercaptopropionic acid; or
Each liter of the prepreg comprises water, 5g to 20g of sulfuric acid, 0.5g to 1g of ethylene diamine tetraacetic acid trisodium salt and 0.5g to 1g of polyethyleneimine; or
Each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 0.5g to 1g of pyridinium hydroxypropanesulfonate, and 1g to 2g of diethylenetriamine; or
Each liter of the prepreg comprises water, 10g to 20g of hydrochloric acid, 1g to 2g of trisodium N-hydroxyethyl ethylenediamine triacetate and 0.5g to 1g of polyethyleneimine; or
Each liter of the prepreg liquid comprises water, 10g to 20g of sulfuric acid, 1g to 2g of 1- (2-hydroxyethyl) imidazole and 0.5g to 1g of 1, 4-butanediamine.
7. The method for preparing the pre-dip solution for inhibiting the electroless plating and bleeding of a copper surface according to any one of claims 1 to 6, characterized by comprising the steps of:
mixing said water, said acidic agent and said pre-soak additive.
8. Use of a pre-dip according to any one of claims 1 to 6 for inhibiting the electroless plating of copper surfaces in electroless nickel plating.
9. A method for chemically plating nickel on a copper surface is characterized by comprising the following steps:
soaking a base material with copper on the surface in a pre-soaking solution for inhibiting the electroless plating and the diffusion plating of the copper surface according to any one of claims 1 to 6 for pre-soaking;
and (4) activating and chemically plating nickel on the base material after the pre-soaking treatment.
10. A method of electroless nickel plating a copper surface as claimed in claim 9 wherein said substrate having a surface comprising copper is a PCB board; the line width of the copper wire on the PCB circuit board and the line distance of the adjacent copper wires are both 60-120 mu m; and/or
The presoaking time is 1 min-5 min; and/or
After the step of electroless nickel plating, the method also comprises the step of performing electroless gold plating on the surface of the nickel.
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| CN114892151A (en) * | 2022-06-21 | 2022-08-12 | 广东哈福科技有限公司 | Ionic palladium activating solution for horizontal copper deposition and preparation method thereof |
| CN115110070A (en) * | 2022-07-13 | 2022-09-27 | 上海天承化学有限公司 | Pre-immersion liquid for ionic palladium activation process and application thereof |
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