CN106917077A - Electroless copper plating solution and electroless copper plating method for increasing hardness of copper plating layer - Google Patents
Electroless copper plating solution and electroless copper plating method for increasing hardness of copper plating layer Download PDFInfo
- Publication number
- CN106917077A CN106917077A CN201611108797.2A CN201611108797A CN106917077A CN 106917077 A CN106917077 A CN 106917077A CN 201611108797 A CN201611108797 A CN 201611108797A CN 106917077 A CN106917077 A CN 106917077A
- Authority
- CN
- China
- Prior art keywords
- agent
- electroless copper
- plating solution
- copper plating
- leveling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010949 copper Substances 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 238000007747 plating Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 99
- -1 thallium ions Chemical class 0.000 claims abstract description 33
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 17
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 11
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 239000011669 selenium Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 45
- 150000002460 imidazoles Chemical class 0.000 claims description 28
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 235000019253 formic acid Nutrition 0.000 claims description 3
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 239000008139 complexing agent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000523 sample Substances 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000002203 pretreatment Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- QPNXDYIIMODUQF-UHFFFAOYSA-N 1,3-dichloropropane-1,2,3-triol Chemical compound OC(Cl)C(O)C(O)Cl QPNXDYIIMODUQF-UHFFFAOYSA-N 0.000 description 1
- HQNBJNDMPLEUDS-UHFFFAOYSA-N 1,5-dimethylimidazole Chemical compound CC1=CN=CN1C HQNBJNDMPLEUDS-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CPKUDYUJOXRCAJ-UHFFFAOYSA-N 2-chloroacetic acid Chemical compound OC(=O)CCl.OC(=O)CCl CPKUDYUJOXRCAJ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- WOHOXHYMCWWJJH-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1.CC1=NC=CN1 WOHOXHYMCWWJJH-UHFFFAOYSA-N 0.000 description 1
- BWDPPMPQZZILAG-UHFFFAOYSA-N 3-(chloromethyl)aniline Chemical compound NC1=CC=CC(CCl)=C1 BWDPPMPQZZILAG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XTXXHBQLHLGHIA-UHFFFAOYSA-N ClC(C)C.ClC(C)C Chemical compound ClC(C)C.ClC(C)C XTXXHBQLHLGHIA-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- NXUQQOMNDNTSEI-UHFFFAOYSA-N [K].N#CO.[Se] Chemical compound [K].N#CO.[Se] NXUQQOMNDNTSEI-UHFFFAOYSA-N 0.000 description 1
- 229920003230 addition polyimide Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- SDFNZYMSEOUVIF-UHFFFAOYSA-N copper;methanesulfonic acid Chemical compound [Cu].CS(O)(=O)=O SDFNZYMSEOUVIF-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- UESISTHQAYQMRA-UHFFFAOYSA-M formyloxythallium Chemical compound [Tl+].[O-]C=O UESISTHQAYQMRA-UHFFFAOYSA-M 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Abstract
An electroless copper plating solution comprising a solvent, copper ions, a complexing agent, a reducing agent, a leveling agent, and a hardening agent, the leveling agent being selected from a polyimide, an imidazole-based quaternary ammonium salt material, or a combination thereof, the hardening agent being selected from thallium ions, tellurium ions, selenium ions, or a combination thereof. The hardness of the plating layer is improved by adding the hardening agent, and the specific leveling agent is selected to force copper ions to be arranged more uniformly, so that the added hardening agent is uniformly distributed around copper crystal grains, and the hardness of the plating layer is further improved.
Description
Technical field
The present invention relates to a kind of copper electrolyte and copper electroplating method, more particularly to a kind of electroless copper plating solution and electroless copper side
Method.
Background technology
Electroless plating (electroless plating), electroplates also known as chemical plating (chemical plating) or self-catalysis
(auto-catalytic plating), it is, in high molecular body surface, in the way of chemistry redox, to form one layer
Thickness enables idioelectric body surface to be switched on about in 0.2 to 2 micron of continuous metal layer, with the operation of sharp follow-up plating.
This kind of copper facing mode, has the advantages that coating is uniform, coating porosity is low, simple to operate, can be plated on non-conductor ..., often in plastics
On carry out, or for the perforation coating of printed circuit board (PCB) (PCB), and MID (Molded Interconnect
Device) processing procedure.
So-called MID processing procedures, are that 3D stereo circuits are carved out on non-conductive substrate by laser carved technology, then,
Again in the way of electroless copper, direct plating goes out (usual more than the copper coating of 8 microns of thickness in foregoing carved out indent circuit
It is 12 microns), the then thin layer gold of coating last layer, silver layer or copper protective agent again, to prevent copper coating from aoxidizing.MID processing procedures are
The antenna manufacture in intelligent mobile phone, iPad or transfer element is widely used in, mainly enough electric fluxes can be provided with sharp signal
Transmission.However, the transmission of mobile phone signals is by original 2G, 3G, to 4G now, requirement of the antenna on precision is got over for evolution
Come more harsh, and in operation, copper coating can be collided and produce indentation unavoidably, or when being assembled again, because of hardness
It is not enough so that coating surface produces defect when being in contact with other elements.However, now use high-frequency signals more, it is walking
On the surface of electric conductor, when surface produces indentation or other defect, detrimental effect will be presented with to antenna.
Electroless plating is that the stacking between metal level of being grown up by the way of chemistry redox, therefore metallic atom is less tight
It is close, and without specific orientation, cause hardness relatively low, the need for having improvement.
The content of the invention
It is an object of the invention to provide a kind of electroless copper plating solution, it can make electroless copper layer with hardness higher.
Electroless copper plating solution of the present invention, comprising solvent, copper ion, misfit agent, reducing agent, leveling agent, and hardening agent.This is whole
Flat agent is selected from polyimides, imidazoles system quaternary ammonium material, or combinations of the above, the hardening agent be selected from thallium ion, tellurium ion, selenium from
Son, or above-mentioned arbitrary combination.
The copper ion is derived from water-soluble mantoquita.Foregoing water-soluble mantoquita is selected from copper sulphate, copper chloride, copper nitrate, methyl
Sulfonic acid copper, or above-mentioned arbitrary combination.
Hardening agent of the present invention belongs to ionic, exists in the form of ion in the plating solution, and can form negative electricity collection
Roll into a ball and be eutectoid out with copper.It is preferred that the thallium ion is derived from formic acid thallium (Thallium formate), the tellurium ion is derived from two
Tellurium oxide (Tellurium dioxide), the plasma selenium is derived from Potassium Selenocyanate (Potassium selenocyanate).
For make coating have more preferably hardness and maintain coating property, it is preferred that the concentration of the hardening agent be 0.001 to
0.1g/L is (i.e.：1 to 100ppm).More preferably, the concentration of the hardening agent be 0.002 to 0.05g/L (i.e.：2 to 50ppm).
The leveling agent can reduce the microcosmic uneven amplitude of coating, make coating surface flat smooth.The present invention is using poly-
, used as leveling agent, itself stabilization is less susceptible to be cleaved or react and lose effect for imines, imidazoles system quaternary ammonium material.Preferably
Ground, the number average molecular weight range of the polyimides is 100 to 3000.The polyimides are such as, but not limited to polyethyleneimine (i.e.：
polyethylenimine).The imidazoles system quaternary ammonium material is such as, but not limited to imidazoles system quarternary ammonium salt compound or imidazoles system season
Ammonium salt polymer.The imidazoles system quarternary ammonium salt compound is such as, but not limited to by the component comprising imidazole compound Yu quaternary amine agent
Carry out the water-soluble products that quaternized (quaterisation) reacts formed.The imidazoles system QAS polymer is for example but not
It is limited to by the formed product of the aggregated reaction of the imidazoles system quarternary ammonium salt compound.The imidazoles system QAS polymer is for example but not
It is limited to imidazoles/epihalohydrin copolymer (i.e.：imidazole/epichlorohydrin copolymer).The imidazoles system
Compound can individually it is a kind of use or mix it is various use, and the imidazole compound be such as, but not limited to imidazoles (imidazole),
1- methylimidazoles (1-methylimidazole), 1- ethyl imidazol(e)s (1-ethylimidazole), 2-methylimidazole (2-
Methylimidazole), 1,5- methylimidazoles (1,5-dimethylimidazole), the methylimidazole (1- of 1- ethyls -2
Ethyl-2-methylimidazole), 1- methoxyl groups imidazoles (1-oxymethylimidazole), or 1- vinyl imidazoles (1-
Vinyl imidazole) etc..The quaternizing agent can individually it is a kind of use or mix it is various use, and the quaternizing agent for example but
It is not limited to epoxychloropropane (epichlorohydrin), chloroacetic acid (monochloroacetic acid), benzyl chloride
(benzyl chloride), chloroacetamide (chloroacetoamide), 3- amido chlorobenzoyl chlorides (3-aminobenzyl
Chloride), glycerin dichlorohydrin (dichloroglycerine), iodomethane (methyl iodide), allyl chloride (allyl
Chloride), dichloroethanes (dichloroethane), or monochloropropane (monochloropropane) etc..With the imidazoles system
The consumption of compound is 1 mole of meter, and the amount ranges of the quaternizing agent are 1 mole to 1.5 moles.The operation of the quaterisation
Temperature range is 40 DEG C to 100 DEG C.The operating time scope of the quaterisation is 0.5 to 4 hour.It is preferred that the leveling agent
Polyimides be polyethyleneimine, the imidazoles system quaternary ammonium material of the leveling agent is imidazoles/epihalohydrin copolymer.
It is preferred that the molecular weight of the leveling agent is between 100 to 3000.More preferably, the molecular weight of the leveling agent be between
200 to 2000.Again more preferably, the molecular weight of the leveling agent is between 150 to 1500.
When the concentration of the leveling agent is less than 0.01g/L, planarization effects are not enough, but concentration is more than can reduce plating after 0.8g/L
The speed that layer is grown up.Therefore, it is preferable that the concentration of the leveling agent be 0.01 to 0.8g/L (i.e.：10 to 800ppm).More preferably should
The concentration of leveling agent be 0.02 to 0.3g/L (i.e.：20 to 300ppm).
When the leveling agent is polyimides, its concentration is preferably 0.01 to 0.2g/L (i.e.：10 to 200ppm), most preferably
0.02 to 0.15g/L is (i.e.：20 to 150ppm).When the leveling agent is imidazoles system quaternary ammonium material, its concentration is preferably
0.02 to 0.8g/L is (i.e.：20 to 800ppm), most preferably 0.05 to 0.3g/L is (i.e.：50 to 300ppm).
The misfit agent is to form misfit thing with metal ion, can effectively improve bath stability, the speed of adjustment metal precipitation
Degree, and improve the property of coating.It is preferred that the misfit agent is selected from tetrasodium salt of EDTA, ethylenediamine tetra-acetic acid (i.e.：
Ethylenediaminetetraacetic acid), N, N, N', N'- tetra--(2- hydroxypropyls)-ethylene diamine is (i.e.：N,N,
N', N'-tetrakis- (2-hydroxypropyl)-ethylenediamine), or sodium potassium tartrate tetrahydrate is (i.e.：Potassium
sodium tartrate)。
When there is gas evolution on thing surface to be plated, to accelerate the discharge of gas, wetting agent can be added to be improved.The wetting
Agent is avoided that gas is carried out side by side with metal deposit, reduces the formation of pin hole.It is preferred that electroless copper plating solution is also comprising wetting
Agent.More preferably, the wetting agent is selected from polyethers, polyalkenylalcohols or ployphosphonate ester (i.e.：Polyphosphoester).The polyethers for example but
It is not limited to polyethylene glycol.The ployphosphonate ester is such as, but not limited to poly- thermally coupled distillation columns (i.e.：
polyoxyethylene nonylphenyl ether branched phosphate)。
In order to stablize plating solution, the activity of plating solution by way of adding stabilization agent, can be controlled, it is to avoid deterioration.It is preferred that nothing
Plating copper electrolyte also includes stabilization agent.The stabilization agent is selected from cyanide (i.e.：Cyanide) or 2,2'- bipyridyls (i.e.：2,2'-
Bipyridine).The cyanide is such as, but not limited to potassium ferrocyanide (Potassium ferrocyanide).
Reducing agent of the present invention can be any component existing in electroless copper.And it is preferred that the reduction
Agent is selected from formaldehyde (i.e.：Formaldehyde), glyoxalic acid is (i.e.：Glyoxylic acid), diamine (i.e.：Hydrazine), boron hydrogen
Change sodium (i.e.：Sodium borohydride), dimethyamine borane (i.e.：Dimethylamine borane), N, N- diethyl
Amine borine is (i.e.：N, N-diethylamine borane), or sodium hypophosphite is (i.e.：Sodium hypophosphite).
Another object of the present invention, that is, providing a kind of electroless copper method for increasing chemical copper hardness, and it can make without electricity
Copper plate has hardness higher.
The present invention increases the electroless copper method of copper coating hardness, comprises the steps of:After a test piece is taken through pre-treatment, then
Electroless copper plating solution as the aforementioned is immersed, with copper coating of growing up.
The control of thickness of coating, is by first calculating the thickness of per unit hour coating growth (i.e.：Coating growth rate),
Thickness of coating is adjusted with the control of soak time again.It is preferred that coating growth rate is 4 to 6 micro- ms/h, and more preferably, plating
Layer growth rate is 4.5 to 5.5 micro- ms/h.The foregoing coating growth rate of correspondence, the soak time of the test piece is controlled 2 to 3
Hour.
The temperature of electroless copper plating solution has influence on the speed of coating growth, when temperature is less than 40 DEG C, grows up slow, and works as
When temperature is higher than 60 DEG C, then there is the problem of power consumption.Therefore, it is preferable that the temperature control of the electroless copper plating solution is at 40 to 60 DEG C.
More preferably, the temperature control of the electroless copper plating solution is at 45 to 55 DEG C.
The beneficial effects of the present invention are：By adding the hardening agent, coating hardness is improved, and again from specific leveling
Agent, forces copper ion to have more consistent arrangement, allows added hardening agent to be distributed evenly in around copper crystal grain, allows coating
Hardness more lifted.
Specific embodiment
Electroless copper plating solution of the present invention, comprising solvent, copper ion, misfit agent, reducing agent, leveling agent, and hardening agent.This is whole
Flat agent is selected from polyimides, imidazoles system quaternary ammonium material, or combinations of the above, the hardening agent be selected from thallium ion, tellurium ion, selenium from
Son, or above-mentioned arbitrary combination.
In alkali plating solution, the hardening agent (thallium ion, tellurium ion, plasma selenium) can form negative electricity group, and be adsorbed in and treat
Plate thing surface and separated out jointly with copper, to increase the hardness of coating.The present invention is again by from polyimides, imidazoles system quaternary ammonium salt material
Material allows it to be adsorbed in thing surface to be plated as leveling agent, forces copper ion to be arranged in more consistent mode on thing surface to be plated,
And promote the hardening agent to be uniformly dispersed, allow the hardness of coating further to be lifted.By electroless copper plating solution institute of the invention
Obtained coating, with hardness higher, Hv values can be more than 170.
The present invention will be described further with regard to following examples, however, it should be noted that the embodiment such as this is only to illustrate
With, and it is not necessarily to be construed as the limitation of present invention implementation.
[embodiment 1]
It is prepared by plating solution
Take the copper chloride of 5.29g (i.e.：Copper ion containing 2.5g) it is put into the beaker of 1L, and the water of 0.6L is added, it is molten
Add tetrasodium salt of EDTA (EDTA-4Na) as misfit agent after solution, stirring adds NaOH to dissolving
(NaOH) adjustment pH value is again heated to 55 DEG C to more than 12.5, is subsequently added the poly- thermally coupled distillation columns of 0.1g
(RHODIA is purchased from, the name of an article isRE-610) as wetting agent, and 2, the 2'- bipyridyls of 0.004g (are purchased from
Merck) as stabilization agent, then, the imidazoles/epihalohydrin copolymer for adding 0.1g (is purchased from BASF, the name of an article isIZE) as leveling agent, and add as hardening agent the common 0.055g of formic acid thallium (i.e.：Contain 0.045g's
Thallium ion), it is the formaldehyde of 24wt% as reducing agent after 16g and concentration expressed in percentage by weight after the dissolving of its grade, is added, and add water to
Make overall volume in plating solution for 1L, be finally putting into copper foil examination plating and activated for 5 minutes, that is, complete the system of electroless copper plating solution
It is standby.
Sample preparation
Test piece pre-treatment step：(length × a width of 5cm × 5cm, thickness are 18.5 microns, Ra=to take an electrolytic copper foil test piece
0.192) catholyte degreaser, is immersed, and degreasing is carried out 5 minutes with the current density of 4ASD at a temperature of 60 DEG C, then
Test piece washing is taken out, soaking concentration is the dilute sulfuric acid 2 minutes of 10v/v% under normal temperature, take out and carry out after the time reaches
Washing, then completes pre-treatment step.
Rate estimation
The test piece of a completion pre-treatment is taken, the foregoing electroless copper plating solution for preparing is immersed into the test piece, in 55 DEG C of temperature
The lower immersion of degree 30 minutes, further takes out the test piece and is cleaned and dried with water, then measures thickness, estimates every 30 minutes copper coatings
The speed of growth.The speed of the present embodiment is about 5.5 to 6 micro- ms/h.
Electroless copper
The test piece of another completion pre-treatment is taken, the foregoing electroless copper plating solution for preparing is immersed into the test piece, in 55 DEG C
At a temperature of soak, often spend 30 minutes i.e. analysis water level, copper ion, the concentration of reducing agent and NaOH, not enough person is to be mended
Fill, treat that the test piece is soaked 2 to 3 hours, in copper coating up to thickness up to after 12 microns, further taking out the test piece and cleaned and dry with water
It is dry.
Sample test
Take the test piece after foregoing copper facing, with nm impressing test system (Nano Indenter, it is limited purchased from Guo Ke enterprises
Company, model：NTS Nano IndenterG200) it is measured.Using probe impression, it is measured when depth reaches 1000nm
Impression, obtains its Hv value.1000Hv=feedback pressure GPa/9.8.After after tested, the Hv values of the layers of copper in the test piece are 208.
[embodiment 2 to 8]
Prepared by the plating solution of this series embodiment, sample preparation and sample test are all similar to Example 1, and difference is only that institute
The reagent type of use is slightly different.The hardening agent that this series embodiment is used is all thallium ion, and leveling agent is selected from miaow
The polyethyleneimine of azoles/epihalohydrin copolymer, molecular weight 1400, and molecular weight 200 polyethyleneimine.The embodiment
Detailed composition and operation temperature be listed in table 1.
This series embodiment as hardening agent, adjusts the concentration of thallium ion and is each aided with different whole all using thallium ion
Flat agent, obtained copper coating Hv values are respectively 202,198,203,200,204,204,212, all higher than 170.
[comparative example 1]
Refering to table 1, this comparative example is roughly the same with embodiment 1, and difference is only that and is not added with leveling agent and hardening agent.Obtained
The copper coating hardness Hv values for obtaining are 108.
[comparative example 2]
Refering to table 1, this comparative example is roughly the same with embodiment 1, and difference is only that and is not added with hardening agent, and leveling agent is to adopt
With IZE, concentration is 0.2g/L.The copper coating hardness Hv values for being obtained are 113.
[comparative example 3]
Refering to table 1, this comparative example is roughly the same with embodiment 1, and difference is only that and is not added with leveling agent, and thallium ion is dense
It is 0.02g/L to spend.The copper coating hardness Hv values for being obtained are 142.
From comparative example 1 to 3, the plating solution without addition leveling agent and hardening agent, obtained coating Hv values only have
108, can increase to 113 after addition leveling agent, and the person that only adds thallium ion, Hv values can increase to 142.Embodiment 1 to 8 is while adding
Plus thallium ion and leveling agent, Hv values are all more than 170, it follows that pass through to select specific leveling agent and hardening agent, can be effective
Improve the hardness of coating.
Table 1
[embodiment 9 to 11]
Prepared by the plating solution of this series embodiment, sample preparation and sample test are all similar to Example 1, and difference is only that institute
The reagent type of use is slightly different.The hardening agent that this series embodiment is used is all tellurium ion, is by adding titanium dioxide
Tellurium and obtain, the concentration of tellurium ion is respectively 0.02,0.015 and 0.01g/L.Leveling agent is common selected from imidazoles/epoxychloropropane
The polyethyleneimine of polymers, molecular weight 140, and molecular weight 200 polyethyleneimine.After sample test, the Hv values point of coating
Wei 206,205,209.The Detailed composition and operation temperature of the embodiment have been listed in table 2.
[embodiment 12 to 14]
Prepared by the plating solution of this series embodiment, sample preparation and sample test are all similar to Example 1, and difference is only that institute
The reagent type of use is slightly different.The hardening agent that this series embodiment is used is all plasma selenium, is by adding selenium cyanic acid
Potassium and obtain, the concentration of tellurium ion is respectively 0.012,0.01g/L.Leveling agent be selected from imidazoles/epihalohydrin copolymer and
The polyethyleneimine of molecular weight 200.After sample test, the Hv values of coating are respectively 203,195,208.The embodiment it is detailed
Thin formula and operation temperature have been listed in table 2.
[comparative example 4]
Refering to table 2, this comparative example is roughly the same with embodiment 1, and difference is only that and is not added with leveling agent, and hardening agent is dense
The tellurium ion (being derived from tellurium dioxide) for 0.015g/L is spent, the copper coating hardness Hv values for being obtained are 154.
[comparative example 5]
Refering to table 2, this comparative example is roughly the same with embodiment 1, and difference is only that and is not added with leveling agent, and hardening agent is dense
The plasma selenium (being derived from Potassium Selenocyanate) for 0.012g/L is spent, the copper coating hardness Hv values for being obtained are 158.
Table 2
Embodiment 9 to 11 is all to use tellurium ion as hardening agent, and embodiment 12 to 14 is as increasing using plasma selenium
Hard agent, previous embodiment is all aided with addition leveling agent, the Hv values scope for being obtained between 195 to 209, more than 170.And comparative example
4 is only to add tellurium ion but the plating solution without leveling agent, and Hv values are 154, and comparative example 5 is only to add plasma selenium but without leveling agent
Plating solution, Hv values be 158.It can thus be appreciated that after addition polyimides, imidazoles system quaternary ammonium material are as leveling agent, more can be further
Improve the hardness of coating.
In sum, the present invention improves coating hardness by adding hardening agent, and selects specific leveling agent again, forces
Copper ion has more consistent arrangement, allows added hardening agent to be distributed evenly in around copper crystal grain, allows the hardness of coating
More lifted, so the purpose of the present invention can be reached really.
Claims (12)
1. a kind of electroless copper plating solution, it is characterised in that include：Solvent, copper ion, misfit agent, reducing agent, leveling agent, and hardening
Agent, the leveling agent is selected from polyimides, imidazoles system quaternary ammonium material, or combinations of the above, the hardening agent be selected from thallium ion, tellurium from
Son, plasma selenium, or above-mentioned any combination.
2. electroless copper plating solution according to claim 1, it is characterised in that：The polyimides of the leveling agent are polyethyleneimine
Amine, the imidazoles system quaternary ammonium material is imidazoles/epihalohydrin copolymer.
3. electroless copper plating solution according to claim 1, it is characterised in that：The thallium ion is derived from formic acid thallium, the tellurium from
Son is derived from tellurium dioxide, and the plasma selenium is derived from Potassium Selenocyanate.
4. electroless copper plating solution according to claim 1, it is characterised in that：The molecular weight of the leveling agent between 100 to
3000。
5. electroless copper plating solution according to any one of claim 1 to 4, it is characterised in that：The concentration of the hardening agent is
0.001 to 0.1g/L.
6. electroless copper plating solution according to any one of claim 1 to 4, it is characterised in that：The concentration of the hardening agent is
0.002 to 0.05g/L.
7. electroless copper plating solution according to any one of claim 1 to 4, it is characterised in that：The concentration of the leveling agent is
0.01 to 0.8g/L.
8. electroless copper plating solution according to claim 7, it is characterised in that：The concentration of the leveling agent is 0.02 to 0.3g/
L。
9. electroless copper plating solution according to claim 7, it is characterised in that：When the leveling agent is polyimides, concentration is
0.01 to 0.2g/L, when the leveling agent is imidazoles system quaternary ammonium material, concentration is 0.02 to 0.8g/L.
10. electroless copper plating solution according to claim 7, it is characterised in that：When the leveling agent is polyimides, concentration is
0.02 to 0.15g/L, when the leveling agent is imidazoles system quaternary ammonium material, concentration is 0.05 to 0.3g/L.
A kind of 11. electroless copper methods for increasing copper coating hardness, it is characterised in that comprise the steps of:Take the premenstrual place of a test piece
After reason, then electroless copper plating solution as claimed in claim 1 is immersed, with copper coating of growing up.
The 12. electroless copper methods for increasing copper coating hardness according to claim 11, it is characterised in that：The electroless copper
The temperature control of plating solution is at 40 to 60 DEG C.
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| TWI606140B (en) | 2017-11-21 |
| CN106917077B (en) | 2019-09-27 |
| TW201723223A (en) | 2017-07-01 |
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