CN117203367A - 以不同电流密度电化学沉积铜的方法 - Google Patents
以不同电流密度电化学沉积铜的方法 Download PDFInfo
- Publication number
- CN117203367A CN117203367A CN202280030487.0A CN202280030487A CN117203367A CN 117203367 A CN117203367 A CN 117203367A CN 202280030487 A CN202280030487 A CN 202280030487A CN 117203367 A CN117203367 A CN 117203367A
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- CN
- China
- Prior art keywords
- copper
- current density
- layer
- copper foil
- rolled
- 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.)
- Pending
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 239000010949 copper Substances 0.000 title claims abstract description 129
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 21
- 239000011889 copper foil Substances 0.000 claims abstract description 81
- 238000000151 deposition Methods 0.000 claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 238000007747 plating Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 15
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 19
- 239000011888 foil Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 125000006294 amino alkylene group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 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 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- LUENVHHLGFLMFJ-UHFFFAOYSA-N 4-[(4-sulfophenyl)disulfanyl]benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1SSC1=CC=C(S(O)(=O)=O)C=C1 LUENVHHLGFLMFJ-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 229920000464 Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- HRMOLDWRTCFZRP-UHFFFAOYSA-L disodium 5-acetamido-3-[(4-acetamidophenyl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].OC1=C(C(=CC2=CC(=CC(=C12)NC(C)=O)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC=C(C=C1)NC(C)=O.[Na+] HRMOLDWRTCFZRP-UHFFFAOYSA-L 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
-
- 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
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
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Abstract
本发明涉及一种用于电化学沉积铜的方法,其包含:‑提供包含第一表面和第二表面的经轧制和退火的铜箔,‑蚀刻所述经轧制和退火的铜箔的所述第一表面,从而产生第一经蚀刻表面,‑通过化学镀铜沉积在所述第一经蚀刻表面上沉积铜,从而在所述第一经蚀刻表面上产生第一化学镀铜层,‑通过电化学沉积在所述第一化学镀铜层上沉积其它铜,从而产生第一电化学铜层,其中在所述电化学沉积中,在第一时段中施加第一电流密度并且在第二时段中施加第二电流密度,其中所述第二电流密度低于所述第一电流密度;以及可通过所述方法获得的分层产品。
Description
技术领域
本发明涉及一种用于将铜电化学沉积于RA箔上的方法,和可通过所述方法获得的分层产品。
背景技术
从印刷电路板领域中的现有技术已知经轧制和退火铜箔,也称为“轧制退火铜箔(rolled annealed copper foil/roll anneal copper foil)”并且下文中也缩写为RA铜箔。RA铜箔应理解为经退火(即,经受退火处理)的轧制铜箔。轧制可通过轧制铜块或铜坯料以获得具有所需厚度的箔来进行,优选在高压下进行。退火可通过加热轧辊进行,其可在非加热轧辊之后布置。经退火铜箔的制造公开于例如US2009173414A1中。
已知RA铜箔用于柔性印刷电路板和小线路。RA铜箔最常用于金属化下一代柔性衬底以作为柔性印刷电路板(FPCB)。
柔性印刷电路板(FPCB)在电子行业中的重要性越来越大。一种获得高度柔性铜箔的方法为轧制-退火(RA)方法,其根据箔(经高度退火,HA型铜箔)的平面产生具有约至多100μm宽的大微晶的微观结构。这些微晶经对齐,其[100]方向沿着轧制方向,并且其[001]方向垂直于箔的表面(立方体纹理)。此微观结构防止在弯曲时应力在晶界处积聚,并且因此通过使初始开裂点最小化来防止金属疲劳。在生产FPCB时,RA箔层压于如聚酰亚胺的柔性聚合物或其它绝缘衬底上。为产生多层柔性电路,需要一连串其它镀铜步骤。在电镀之前,使用化学镀在电绝缘的部分表面上沉积铜。
然而,特殊晶体结构,尤其对于“超柔性”HA铜箔,需要复杂的电镀溶液以便实现所需表面形态。一项主要挑战为电解镀铜步骤之后的表面外观。表面必须具有某种有光泽外观,以便在结构化期间实现均匀蚀刻并且确保可靠的自动光学检验(AOI)。
半蚀刻工艺之后,RA箔的晶体结构展示宏观非均匀表面。此导致在化学镀和随后电化学镀Cu之后的无光泽Cu表面。
AOI和后续处理步骤需要有光泽Cu表面。同时,必须填充如盲微孔(BMV)和通孔(THF)的结构(如果存在)。对于此类填充,通常至少在电化学铜沉积开始时使用低电流密度。然而,通过此方法,仅达到无光泽表面外观。据信无光泽表面由蚀刻RA箔的预处理引起,所述RA箔具有如上文描述的宏观非均匀表面。
发明目标
本发明的问题为提供一种用于在包含RA铜层、化学镀铜层和电化学沉积铜层的产品中产生更有光泽或光滑的铜表面的方法。
发明内容
本发明提供一种用于电化学沉积铜的方法,其包含
-提供包含第一表面和第二表面的经轧制和退火铜箔,
-蚀刻所述经轧制和退火铜箔的所述第一表面,从而产生第一经蚀刻表面,
-通过化学镀铜沉积在所述第一经蚀刻表面上沉积铜,从而在所述第一经蚀刻表面上产生第一化学镀铜层,
-通过电化学沉积在所述第一化学镀铜层上沉积其它铜,从而产生第一电化学铜层,其中在所述电化学沉积中,在第一时段中施加第一电流密度并且在第二时段中施加第二电流密度,其中所述第二电流密度低于所述第一电流密度。
本发明进一步提供一种分层产品,其包含:
-包含第一经蚀刻表面和第二表面的经轧制和退火铜箔,
-第一化学镀铜层,其存在于所述经轧制和退火铜箔的所述第一经蚀刻表面上,
-第一电化学铜层,其存在于所述第一化学镀铜层上,
其中所述第一电化学铜层具有在60°入射角下具有至少400光泽单位的光泽度的外表面。
本发明的解决方案为施加至少两种不同电流密度
1.高起始电流密度持续短时间。在不希望受理论束缚的情况下,据信此处形成薄屏障层,其避免即使在下一层(第一电化学沉积铜层)中也保持RA铜上第一化学镀铜层的无光泽度。
2.较低电镀电流密度持续第二时段,优选地为电化学铜沉积的剩余时间。此处,结构(如果存在)填充有铜,并且达到铜在包括结构的整个区域上方的分布,其中分布可为均匀的,并且结构可经填充而无凹痕或过度填充。
在其一般或在特定实施例中,本发明提供以下优点中的一或多者:
-已展示通过本发明的方法可获得电化学沉积铜的光滑/有光泽的表面。
-所达到的光泽度有益于铜表面的检验、表面的外观和用于其它方法步骤,例如通过例如半加成方法将铜表面结构化。
-本发明的方法适合于生产用于柔性印刷电路板的前体产品。
-无气泡的化学镀铜沉积
-本发明的方法实现良好的覆盖范围和较厚的化学镀铜沉积物,而且是在关键点处,例如盲微孔(BMV)角落或在通孔内的暴露粘着层上
-本发明的方法允许即使在如由PI制成的支撑层的光滑衬底上也实现化学镀沉积铜层的极佳并且无气泡的粘着。
附图说明
图1展示用于制造RA箔的方法流程图;
图2展示在不同衬底上的铜沉积方法的流程图;
图3展示根据本发明的实例相较于比较实例中光泽度的实验数据。
具体实施方式
现将详细参考实施例,其实例在附图中示出。将参考附图描述示范性实施例的效果和特征及其实施方法。如本文所用,术语“和/或”包括一或多个相关联的所列项目的任何和所有组合。另外,在描述本发明的实施例时,“可”的使用是指“本发明的一或多个实施例”。
在本发明的实施例的以下描述中,除非上下文另外明确地指示,否则单数形式的术语可包括复数形式,例如如果使用‘铜箔(copper foil)’,那么包括‘铜箔(copperfoils)’。
RA铜箔应理解为经轧制和退火(即,经受轧制和退火处理)的铜箔。优选地,所获得的晶体形状为层状结构,并且由根据箔平面的粒度为100μm的巨大晶体组成。优选地,RA铜将具有平行于加工方向的长型晶粒结构或长型晶体结构,所述加工方向为轧制工艺的方向,即铜箔的输送方向。优选地,经轧制和退火的铜箔包含经对齐的铜微晶,其[100]方向沿着轧制方向,并且其[001]方向垂直于箔的表面(立方体纹理[100])。轧制可通过轧制铜块或铜坯料以获得具有所需厚度的箔来进行,优选在高压下进行。退火可通过加热轧辊进行,所述加热轧辊可在非加热轧辊之后布置。本发明不涉及并非由铜块或铜坯料制成的铜箔,尤其在本发明的意义上排除如由电流方法制成的ECD铜箔形式的铜箔。
术语RA铜箔应理解为涵盖所谓高度退火的铜箔,下文也简称为HA铜箔。HA铜箔具有较大的晶粒和高度均一的晶向。HA铜箔展示极高柔性。
在应用蚀刻步骤之前,经轧制和退火的铜箔优选具有6到30μm、更优选10到20μm、甚至更优选12到18μm的厚度。
在一个实施例中,在进行蚀刻步骤之前,所提供的经轧制和退火的铜箔与支撑层层压以获得层压衬底。在此实施例中,支撑层可包含第一表面和第二表面。这意味着在蚀刻步骤之前,所提供的经轧制和退火的铜箔的第二表面与支撑层的第一表面层压以获得层压衬底。支撑层优选地为柔性非导电塑料层,更优选为塑料箔。柔性非导电塑料层例如选自如聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚碳酸酯(PC)、液晶聚合物(LCP)和环烯烃共聚物(COC)等柔性非导电聚合物。柔性非导电塑料层可为柔性塑料复合层或前述聚合物的共混层,更优选为聚酰亚胺或聚酰亚胺的共混物。
在另一实施例中,可将另一经轧制和退火的铜箔层压于所述支撑层的第二表面上(所述支撑层的第二表面可与所述另一经轧制和退火的铜箔的第一表面层压)。在此情况下,本发明的方法可用层压于支撑层的所述两个表面上的两个经轧制和退火的铜箔来进行,以便获得层压衬底。
所获得的一或两个铜箔与一个支撑层的层压衬底可用作用于制造例如移动电话中的柔性电路板的前体产品。
支撑层优选具有20到70μm的厚度,更优选为30到50μm。
在一个实施例中,经轧制和退火铜箔的厚度为6到30μm。铜箔层压于厚度为20到70μm的聚酰亚胺支撑层上。
在一个实施例中,层压衬底(包含一个或两个铜箔)可例如通过激光钻孔而结构化以获得盲微孔和任选的通孔。在结构化之后,层压衬底包含穿过铜箔并且终止于层压支撑层上的盲微孔,并且任选地包含完全贯穿铜箔和支撑层的通孔。换句话说,层压衬底包含从铜箔的第一表面穿过并且终止于支撑层的第一表面上或支撑层内的盲微孔,并且任选地包含完全贯穿铜箔和支撑层的通孔。结构化可后接去污工艺,并且结构化可在蚀刻步骤之前或在蚀刻步骤之后进行。
在一个实施例中,盲微孔的宽度与深度之比为约1:2到约2.5:1。优选宽度介于50到150μm的范围内,并且优选深度介于30到100μm的范围内,更优选地,盲微孔具有介于100与40μm直到70与30μm范围内的宽度与深度之比。
在通孔的情况下,优选纵横比(宽度与深度)为1到3,优选1到1.5。优选宽度介于50到80μm的范围内,更优选为70μm,并且优选深度介于100到200μm的范围内,更优选为110μm。
蚀刻:
蚀刻RA铜箔的表面也称为“半蚀刻”。在此步骤中,部分去除RA铜箔的铜,其中形成粗糙铜表面。
蚀刻步骤通过已知蚀刻溶液进行,其可包含氧化剂,例如有机或无机过氧化物和无机酸,如硫酸或盐酸,例如优选蚀刻溶液包含过氧化氢和硫酸。另外,蚀刻溶液可包含一或多种添加剂和一或多种卤化物以维持蚀刻稳定性。可使用包含H2O2/H2SO4和氯离子的标准蚀刻溶液。
蚀刻溶液可通过例如喷涂或浸没来施加。
在蚀刻步骤期间,铜层的厚度优选地减少2到10μm,更优选减少3到6μm。
化学镀铜沉积
在蚀刻步骤之后,通过已知的化学镀水溶液进行化学镀铜沉积步骤,所述已知水溶液例如公开于EP 2784181 B1中。化学镀铜溶液将最有效地在经蚀刻的经轧制和退火铜箔的表面上形成铜,优选纯铜层(纯意指99重量%或更高的铜含量),或铜合金层,优选铜层(第一化学镀铜层)。
一般来说,化学镀溶液包含如硫酸铜、氯化铜、硝酸铜、乙酸铜、甲磺酸铜、氢氧化铜的铜离子来源;用于铜或合金金属离子的还原剂和络合剂来源。还原剂的来源可为甲醛、多聚甲醛、乙醛酸、NaBH4、KBH4、NaH2PO2、肼、福尔马林、多糖(例如葡萄糖)和其混合物,并且络合剂的来源可为乙二胺四乙酸(EDTA)、N'-(2-羟乙基)-乙二胺、N,N,N'-三乙酸(HEDTA)、环己二胺四乙酸、二亚乙三胺五乙酸和N,N,N',N'-四(2-羟丙基)乙二胺(Quadrol)。其它任选的组分为无机酸或碱、稳定剂、共溶剂、润湿剂和其它功能性添加剂,例如光亮剂、促进剂、抑制剂、抗失泽剂。此类溶液和组分为所属领域中已知的。化学镀铜浴可进一步包含合金金属离子来源,如镍离子或钴离子及其混合物。
化学镀铜溶液为公众已知的并且可购买,例如购自安美特德国公司(AtotechDeutschland GmbH)。
典型的化学镀铜溶液还可包含镍离子并且可添加氰离子。电镀溶液通过充气稳定,并且在沉积期间用电磁搅拌器搅拌溶液。通过电镀30分钟调节新近制备的电镀溶液。
优选通过使经蚀刻的表面与用于化学镀铜沉积的铜溶液(也称为铜浴)接触来进行化学镀沉积。
铜的电化学沉积
对于铜的电化学沉积,优选地使用含水酸性铜电镀浴。此类浴从现有技术已知,例如EP2922985和EP3511444。
第二电流密度低于第一电流密度的表述优选意指第二电流密度比第一电流密度低至少0.2ASD或更多(安培/平方分米;A/dm2),优选低至少0.2到0.5ASD。
第一电流密度和/或第二电流密度可变化,其中第二电流密度始终低于第一电流密度。第一电流密度和/或第二电流密度可具有下降或倾斜斜坡的形状。在第一电流密度和/或第二电流密度变化的情况下,优选第二电流密度的最高值比第一电流密度的最低值低至少0.2ASD或更多,优选低至少0.2到0.5ASD。
第二时段可紧跟在第一时段后。
在第一时段转换到第二时段时,第一电流密度与第二电流密度之间的差值可为至少0.2ASD或更多,优选至少0.2到0.5ASD。
在一个实施例中,第二电流密度在第一电流密度的5%到80%、优选20%到70%、更优选30%到40%范围内。
在一个实施例中,第二电流密度在0.5到2.1ASD、优选0.8到1.6ASD、更优选1.0到1.3ASD范围内。
在一个实施例中,第一电流密度在1到10ASD、优选1到4ASD范围内。如可见,第一电流密度/第二电流密度的优选范围可重叠。然而,根据本发明,第二电流密度始终低于第一电流密度。因此,如果例如第一电流密度选择为1ASD,那么第二电流密度低于1ASD。
在一个实施例中,第一时段的长度在第二时段的长度的1%到25%、优选1%到10%范围内,更优选为第二时段的长度的8%。
在一个实施例中,第一时段在0.5到5分钟、优选1到4分钟、更优选2到4分钟范围内。
在一个实施例中,第二时段在20到60分钟、优选30到40分钟范围内,最优选50分钟。
可参考盲微孔或通孔的几何形状设定第一电流密度的量值,其中在较小结构、尤其具有较小宽度或较小宽度与深度之比的结构的情况下,优选选择较低第一电流密度,并且反之亦然。
在一个实施例中,使用用于沉积的电化学铜溶液,其包含
-铜离子来源,
-酸
-整平剂添加物,和
-任选的以下组分中的一或多者:促进剂-光亮剂添加物、载剂-抑制剂添加物和/或卤素离子。
溶液(也称为含水酸性铜电镀浴)优选地具有≤2、更优选≤1的pH值。
铜离子来源优选选自包含硫酸铜和烷基磺酸铜(例如甲磺酸铜)的群组。含水酸性铜电镀浴中的铜离子浓度优选在4g/l到90g/l范围内,更优选在10g/L到70g/L范围内,再更优选在30g/L到65g/L范围内。
酸优选选自包含硫酸、氟硼酸、磷酸和甲磺酸的群组,并且优选以10g/l到400g/l、更优选20g/l到300g/l、再更优选30g/L到300g/L的浓度添加。
整平剂添加物优选选自一或多种选自由以下组成的群组的化合物:亚脲基聚合物、含氮有机化合物(例如聚乙二亚胺、烷氧基化聚乙二亚胺、烷氧基化内酰胺及其聚合物、二亚乙基三胺和六亚甲基四胺、带有聚乙烯亚胺的肽、带有聚乙烯亚胺的氨基酸、带有聚乙烯醇的肽、带有聚乙烯醇的氨基酸、带有聚亚烷基二醇的肽、带有聚亚烷基二醇的氨基酸、带有氨基亚烷基的吡咯和带有氨基亚烷基的吡啶、脲基聚合物)、有机染料(例如詹纳斯(Janus)绿B、俾斯麦(Bismarck)棕Y和酸性紫7)、含硫氨基酸(例如半胱氨酸)、啡离子盐及其衍生物。所述任选的整平剂添加物以0.1mg/l到100mg/l的量(总量)添加到含水酸性铜电镀浴中。所提及的亚脲基聚合物优选为如EP2922985A中所公开的亚脲基聚合物。
促进剂-光亮剂添加物优选选自一或多种选自由以下组成的群组的化合物:有机硫醇化合物、硫化物化合物、二硫化物化合物和聚硫化物化合物,优选选自由以下组成的群组:3-(苯并噻唑基-2-硫代)-丙基磺酸、3-巯基丙烷-1-磺酸、亚乙基二硫代二丙基磺酸、双(对磺基苯基)-二硫化物、双(ω-磺丁基)-二硫化物、双(ω-磺羟丙基)-二硫化物、双(ω-磺丙基)-二硫化物、双(ω-磺丙基)-硫化物、甲基-(ω-磺丙基)-二硫化物、甲基-(ω-磺丙基)-三硫化物、O-乙基-二硫代碳酸-S-(ω-磺丙基)酯、硫代乙醇酸、硫代磷酸-O-乙基-双(ω-磺丙基)酯、3-N,N-二甲基氨基二硫代氨基甲酰基-1-丙磺酸、3,3'-硫代双(1-丙磺酸)、硫代磷酸-三(ω-磺丙基)酯及其对应盐。任选地存在于含水酸性铜浴组合物中的所有促进剂-光亮剂添加物的浓度(总计)优选在0.01mg/l到100mg/l范围内,更优选在0.05mg/l到10mg/l范围内,再更优选在0.1mg/L到5mg/L范围内。
载剂-抑制剂添加物优选选自一或多种选自由以下组成的群组的化合物:聚乙烯醇、羧甲基纤维素、聚乙二醇、聚丙二醇、硬脂酸聚二醇酯、烷氧基化萘酚、油酸聚二醇酯、硬脂酰基醇聚二醇醚、壬基酚聚二醇醚、辛醇聚亚烷基二醇醚、辛二醇-双-(聚亚烷基二醇醚)、聚(乙二醇-无规-丙二醇)、聚(乙二醇)-嵌段-聚(丙二醇)-嵌段-聚(乙二醇),和聚(丙二醇)-嵌段-聚(乙二醇)-嵌段-聚(丙二醇)。所述任选的载剂-抑制剂添加物的浓度(总计)优选在0.005g/l到20g/l范围内,更优选在0.01g/L到20g/L范围内,再更优选在0.01g/l到5g/l范围内。
任选的卤化物离子优选选自Cl、Br和/或I。在氯化物的情况下,卤化物离子优选以10mg/L到200mg/L,更优选20mg/L到80mg/L或30mg/L到60mg/L添加。如果选择其它卤化物离子,那么优选选择相应摩尔量,或如果选择不同卤化物,那么选择相应总摩尔量。
在根据本发明的方法中,优选地在15℃到50℃范围内的温度下,更优选地在25℃到40℃范围内的温度下通过将电流施加到衬底和至少一个阳极,操作含水酸性铜电镀浴。
如果需要,可在上述步骤之间进行额外步骤作为冲洗步骤,例如使用DI水、清洁器的步骤;预浸渍步骤;和/或干燥步骤。
本发明的方法可包含以下步骤中的一或多者,按任何次序
-自动光学检验
-通过使用已知光刻方法将铜表面结构化
-另一蚀刻步骤
-沉积一或多个其它金属层,例如Cu、Ni、Au等。
在另一方面,本发明涉及通过本发明的方法获得或可获得的分层产品。
在分层产品的一个实施例中,电化学沉积铜层具有沿RA铜箔的加工方向(MD)测量在60°入射角下具有至少400光泽单位的光泽度的外表面。用于测量光泽度的方法在实例部分中给出。光泽度优选为400到800光泽单位、更优选400到600光泽单位、再更优选400到500光泽单位。
在另一方面中,本发明提供一种分层产品,其包含:
-包含第一经蚀刻表面和第二表面的经轧制和退火铜箔,
-第一化学镀铜层,其存在于所述经轧制和退火铜箔的所述第一经蚀刻表面上,
-第一电化学铜层,其存在于所述第一化学镀铜层上,
其中所述第一电化学铜层具有一外表面,所述外表面沿RA铜箔的加工方向(MD)测量在60°入射角下具有至少400光泽单位的光泽度。用于测量光泽度的方法在实例部分中给出。光泽度优选为400到800光泽单位、更优选400到600光泽单位、再更优选400到500光泽单位。
以60°的反射角反射的光束的强度可使用例如毕克化学仪器公司(BYK-GardnerGmbH)的Micro Gloss 60°光泽计测量,其符合DIN 67530、ISO 2813、ASTM D523和BS3900D5部分。
此产品可根据本发明方法获得或可获得。因此,关于本方法所描述的所有特征可单独或组合地为产品的特征。另一方面,本发明的方法可包含关于产品描述的一或多个特征。
第一化学镀铜层可通过化学镀铜沉积获得或可获得,其已于先前描述。
第一电化学铜层可通过电化学铜沉积获得或可获得,其已于先前描述。在通过电化学沉积制备所述第一电化学铜层时,在第一时段施加第一电流密度并且在第二时段施加第二电流密度,其中所述第二电流密度低于所述第一电流密度。在这方面,我们还参考上文对方法和电流密度的描述。
第一化学镀铜层优选地具有0.1μm到4μm、更优选0.2μm到2μm的厚度。
第一电化学铜层优选具有2μm到15μm、更优选4μm到12μm、最优选5μm到10μm的厚度。
第一电化学铜层优选比第一化学镀铜层厚。第二铜层与第一铜层的厚度的比优选在30:1到3:1范围内。
可将经轧制和退火铜箔层压到支撑层,其优选为柔性非导电塑料层,例如聚酰亚胺层,如先前所描述。因此,在分层产品的一个实施例中,经轧制和退火铜箔的第二表面与支撑层的第一表面层压。在这方面,我们参考关于支撑层的先前公开内容。在此实施例中,分层产品可用作柔性电路板的前体产品。
实例
光泽度的测定:
如下测量光泽度。测量光束沿着RA铜箔的加工方向(MD)以60°的入射角施加到经表面处理的电解铜箔的表面。加工方向为轧制工艺的方向,即铜箔的输送方向。以60°的反射角反射的光束的强度使用毕克化学仪器公司的Micro Gloss 60°光泽计测量,其符合DIN67530、ISO 2813、ASTM D523和BS 3900D5部分。
图1显示用于制造RA箔的方法流程图。在减径轧辊2之间引入铜锭1以减少厚度。接着将所获得的箔引入于加热轧辊之间以供退火,并且接着获得RA铜箔4且将其卷起。
图2展示根据现有技术,在不同衬底上的铜沉积方法的流程图。流程图中上面的一行展示铜沉积于通过电化学沉积制成的铜箔5(ECD铜箔5)上。下面的一行展示铜在RA铜箔6上的沉积。在第一步骤A(其在本发明的方法中并非必选的)中,ECD铜箔5和RA铜箔6经层压到塑料箔7(例如聚酰亚胺箔)上。接着,进行所谓的半蚀刻步骤B,在铜上产生粗糙表面。可看出,由于RA铜的特定结构(具有定向于轧制方向上的大晶体/晶粒结构),经蚀刻的RA铜箔6上的表面比经蚀刻的ECD铜箔5上的表面更加不均匀。由于铜晶体结构及其原始生产方法,在半蚀刻工艺B之后,RA/HA箔的晶体结构展示宏观尺度的非均匀表面。在下一步骤C中,进行化学镀铜沉积,并且获得薄化学镀铜层8。从而保持RA铜箔6上的非均匀表面结构。在最后步骤D中,通过电化学沉积以一个电流密度沉积铜并且获得铜层9。从而,在蚀刻B之后的RA铜箔6上的不均匀表面结构仍保持并且延续到铜层9的表面上。
如果产生盲微孔或沟槽,那么此在步骤A之后并且在B之前(即,在半蚀刻之后)或在步骤B之后并且在步骤C之前(在化学镀铜沉积之前)进行。接着可应用清洁和激活步骤(例如用Pd)。
实例1(比较)
比较实例示意性地展示于图2中下面的一行中。
用以下溶液进行RA铜箔的蚀刻B:150ml/L 50% H2SO4、120ml/L 30% H2O2、2mg/L氯化物(NaCl)。
接着,用以下铜浴进行化学镀铜沉积C:
表1:浴和操作条件:
用从EP 2922985 A已知的酸性铜浴进行铜的电化学沉积D,所述酸性铜浴为:含水酸性铜电解质,其包含55g/L铜离子、50g/L硫酸、50mg/L氯离子、3ml/L SPS。
电化学沉积以0.7ASD进行4分钟并且以1.3ASD进行48分钟。
实例2(比较)
与实例1中使用相同的程序,不同之处在于以1.3ASD进行电化学沉积50分钟。
实例2(本发明)
除电化学沉积以2.6ASD(第一电流密度)进行4分钟(第一时段)并且接着以1.3ASD(第二电流密度)进行42分钟(第二时段)以外,使用与实例1和2相同的程序。
结果
根据上文描述的方法测量光泽度。
在图3中展示结果。从左到右展示实例1、实例2和实例3。可看到,在本发明的实例中,达到约425单位的外部铜表面的光泽度,而分别地,在实例1中仅达到约60单位的光泽度,并且在实例2中仅达到约120单位的光泽度。这些结果证明本发明的效果,当在第一时段中施加第一电流密度并且在第二时段中施加第二电流密度时,其中第二电流密度低于第一电流密度,可获得具有较高光泽度的表面。
另外,可发现:
-起始(4分钟)电流密度越高,光泽度越高
-经半蚀刻的样品比未经蚀刻的样品对参数变化更加敏感。
Claims (15)
1.一种用于电化学沉积铜的方法,其包含以下步骤:
-提供包含第一表面和第二表面的经轧制和退火的铜箔,
-蚀刻所述经轧制和退火的铜箔的所述第一表面,从而产生第一经蚀刻表面,
-通过化学镀铜沉积在所述第一经蚀刻表面上沉积铜,从而在所述第一经蚀刻表面上产生第一化学镀铜层,
-通过电化学沉积在所述第一化学镀铜层上沉积其它铜,从而产生第一电化学铜层,其中在所述电化学沉积中,在第一时段中施加第一电流密度并且在第二时段中施加第二电流密度,其中所述第二电流密度低于所述第一电流密度。
2.根据权利要求1所述的方法,其中第二电流密度在所述第一电流密度的1%到50%范围内。
3.根据权利要求1或2所述的方法,其中第二电流密度在0.5ASD到2.1ASD范围内。
4.根据前述权利要求中任一权利要求所述的方法,其中第一电流密度在1ASD到10ASD范围内。
5.根据前述权利要求中任一权利要求所述的方法,其中所述第一时段的长度在所述第二时段的长度的1%到25%范围内。
6.根据前述权利要求中任一权利要求所述的方法,其中所述第一时段在0.5分钟到5分钟范围内。
7.根据前述权利要求中任一权利要求所述的方法,其中所述第二时段在20分钟到45分钟范围内。
8.根据前述权利要求中任一权利要求所述的方法,其中在蚀刻步骤之前,所提供的经轧制和退火的铜箔的所述第二表面与支撑层的第一表面层压以获得层压衬底。
9.根据权利要求8所述的方法,其中所述层压衬底的所述铜箔包含盲微孔,其从所述铜箔的所述第一表面穿过并且终止于支撑层的所述第一表面上或所述支撑层内,并且任选地包含通孔,其完全贯穿所述铜箔和所述支撑层。
10.根据权利要求9所述的方法,其中所述盲微孔具有1:2到2.5:1的宽度与深度的比。
11.根据权利要求9所述的方法,其中所述盲微孔具有50μm到150μm的宽度和30μm到100μm的深度。
12.根据权利要求8至11中任一权利要求所述的方法,其中所述支撑层为柔性非导电塑料层。
13.根据权利要求8至12中任一权利要求所述的方法,其中所述支撑层具有20μm到70μm的厚度。
14.一种分层产品,其包含:
-包含第一经蚀刻表面和第二表面的经轧制和退火的铜箔,
-第一化学镀铜层,其存在于所述经轧制和退火的铜箔的所述第一经蚀刻表面上,
-第一电化学铜层,其存在于所述第一化学镀铜层上,
其中所述第一电化学铜层具有在60°入射角下具有至少400光泽单位的光泽度的外表面。
15.根据权利要求14所述的分层产品,其中所述经轧制和退火的铜箔的所述第二表面与支撑层的第一表面层压。
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