TW202415167A - Metal foil, carrier with metal layer comprising the same and printed circuit board comprising the same - Google Patents
Metal foil, carrier with metal layer comprising the same and printed circuit board comprising the same Download PDFInfo
- Publication number
- TW202415167A TW202415167A TW112121525A TW112121525A TW202415167A TW 202415167 A TW202415167 A TW 202415167A TW 112121525 A TW112121525 A TW 112121525A TW 112121525 A TW112121525 A TW 112121525A TW 202415167 A TW202415167 A TW 202415167A
- Authority
- TW
- Taiwan
- Prior art keywords
- metal layer
- protrusions
- metal
- protrusion
- layer
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 222
- 239000002184 metal Substances 0.000 title claims abstract description 222
- 239000011888 foil Substances 0.000 title claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 238000007772 electroless plating Methods 0.000 claims abstract description 21
- 230000003746 surface roughness Effects 0.000 claims description 13
- 238000009713 electroplating Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 181
- -1 nitrogen-containing compound Chemical class 0.000 description 20
- 230000008054 signal transmission Effects 0.000 description 17
- 230000007423 decrease Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- GVONPBONFIJAHJ-UHFFFAOYSA-N imidazolidin-4-one Chemical compound O=C1CNCN1 GVONPBONFIJAHJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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 3
- 239000002356 single layer Substances 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- NYHBQMYGNKIUIF-UUOKFMHZSA-N Guanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O NYHBQMYGNKIUIF-UUOKFMHZSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- FDGQSTZJBFJUBT-UHFFFAOYSA-N hypoxanthine Chemical compound O=C1NC=NC2=C1NC=N2 FDGQSTZJBFJUBT-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VSOSXKMEQPYESP-UHFFFAOYSA-N 1,6-naphthyridine Chemical compound C1=CN=CC2=CC=CN=C21 VSOSXKMEQPYESP-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- 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
- KFDNQUWMBLVQNB-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KFDNQUWMBLVQNB-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- OHJPGUSXUGHOGE-UHFFFAOYSA-N 2-methyl-6-(6-methylpyridin-2-yl)pyridine Chemical group CC1=CC=CC(C=2N=C(C)C=CC=2)=N1 OHJPGUSXUGHOGE-UHFFFAOYSA-N 0.000 description 1
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- MIKUYHXYGGJMLM-GIMIYPNGSA-N Crotonoside Natural products C1=NC2=C(N)NC(=O)N=C2N1[C@H]1O[C@@H](CO)[C@H](O)[C@@H]1O MIKUYHXYGGJMLM-GIMIYPNGSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 101100201843 Cyprinus carpio rsph1 gene Proteins 0.000 description 1
- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UGQMRVRMYYASKQ-UHFFFAOYSA-N Hypoxanthine nucleoside Natural products OC1C(O)C(CO)OC1N1C(NC=NC2=O)=C2N=C1 UGQMRVRMYYASKQ-UHFFFAOYSA-N 0.000 description 1
- 101100328516 Mus musculus Cnpy2 gene Proteins 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- UXCWQGQTBWILMA-UHFFFAOYSA-N OC(CNCCNCCN)(C(O)(O)O)O Chemical compound OC(CNCCNCCN)(C(O)(O)O)O UXCWQGQTBWILMA-UHFFFAOYSA-N 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000016693 dipotassium tartrate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 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
- 229940029575 guanosine Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by 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
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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Abstract
Description
本發明涉及一種具有粗糙表面的金屬層、一種包括該金屬層的載體貼附金屬箔及一種使用該金屬層製造的印刷電路板。The present invention relates to a metal layer with a rough surface, a carrier-attached metal foil comprising the metal layer, and a printed circuit board manufactured using the metal layer.
印刷電路板典型地透過將金屬箔結合到絕緣樹脂基材,並進行用於電路佈線的金屬箔蝕刻來製造。金屬箔和絕緣樹脂基材之間需要有高黏附強度以避免在電路佈線期間金屬箔剝落。Printed circuit boards are typically manufactured by bonding a metal foil to an insulating resin substrate and performing etching of the metal foil for circuit wiring. High adhesion strength is required between the metal foil and the insulating resin substrate to prevent the metal foil from peeling off during circuit wiring.
有許多提議已被提出以提升金屬箔和絕緣樹脂基材之間的黏附力。例如,透過使金屬箔表面粗糙以在其上形成不規則性,將絕緣樹脂基材放置在金屬箔的不規則表面上,並壓合絕緣樹脂基材以將絕緣樹脂基材結合到金屬箔,金屬箔和絕緣樹脂基材之間的黏附強度增加。具體地,專利文件1(韓國專利公開案第2018-0019190號)揭示了一種透過在樹脂層側面處之銅箔表面的電解、噴砂或氧化還原以形成顆粒突出物來提升銅箔和樹脂層之間黏附力的方法。Many proposals have been made to improve the adhesion between a metal foil and an insulating resin substrate. For example, by roughening the surface of a metal foil to form irregularities thereon, placing an insulating resin substrate on the irregular surface of the metal foil, and pressing the insulating resin substrate to bond the insulating resin substrate to the metal foil, the adhesion strength between the metal foil and the insulating resin substrate is increased. Specifically, Patent Document 1 (Korean Patent Publication No. 2018-0019190) discloses a method for improving the adhesion between a copper foil and a resin layer by electrolyzing, sandblasting, or oxidation-reduction of a copper foil surface at a side of a resin layer to form particle protrusions.
然而,此方法存在一個問題,即額外使金屬箔粗糙化會降低印刷電路板的製造效率。進一步,金屬箔表面不規則性的形成可能會降低高頻訊號的傳輸效率。隨著朝向更高的攜帶式電子裝置性能之趨勢,為了快速處理大量資訊,需要將高頻訊號傳輸的損失最小化。然而,這些不規則性使金屬箔表面高度粗糙,並且作為高頻訊號傳輸的阻礙,造成高頻訊號傳輸效率不佳。However, this method has a problem in that additionally roughening the metal foil reduces the manufacturing efficiency of the printed circuit board. Furthermore, the formation of irregularities on the surface of the metal foil may reduce the transmission efficiency of high-frequency signals. With the trend toward higher performance of portable electronic devices, in order to quickly process a large amount of information, it is necessary to minimize the loss of high-frequency signal transmission. However, these irregularities make the surface of the metal foil highly rough and act as an obstacle to the transmission of high-frequency signals, resulting in poor high-frequency signal transmission efficiency.
習知技術文件 專利文件 (0001) 韓國專利公開案第10-2018-0019190號 (0002) 韓國專利公開案第10-2021-0016322號 Knowledge and technology documents Patent documents (0001) Korean Patent Publication No. 10-2018-0019190 (0002) Korean Patent Publication No. 10-2021-0016322
技術問題 本發明旨在提供與一絕緣樹脂基材具有高黏附強度的一種金屬層,並且能夠避免高頻訊號傳輸效率降低。 本發明也旨在提供包括一金屬層的一載體貼附金屬箔。 本發明也旨在提供包括該金屬層的一印刷電路板。 Technical Problem The present invention aims to provide a metal layer having high adhesion strength to an insulating resin substrate and capable of avoiding reduction in high-frequency signal transmission efficiency. The present invention also aims to provide a carrier-attached metal foil comprising a metal layer. The present invention also aims to provide a printed circuit board comprising the metal layer.
技術手段 本發明的一個態樣提供一種金屬層,其包括複數個頂部平坦的突出物,該等突出物中的每一個包括一凸起及一高台,該凸起具有截頂圓錐或是多角形截頂金字塔的形狀,該高台形成於該凸起的上端處,該等突出物透過無電電鍍形成,並且該金屬層具有1 μm或更少的厚度,其中該凸起具有複數個微突出物,該等微突出物形成於該凸起的高台以外之側表面上,以由於其增加的表面積而提升對一絕緣樹脂基材的黏附力。 Technical means One aspect of the present invention provides a metal layer, which includes a plurality of protrusions with flat tops, each of the protrusions includes a projection and a plateau, the protrusion has a shape of a truncated cone or a polygonal truncated pyramid, the plateau is formed at the upper end of the protrusion, the protrusions are formed by electroless plating, and the metal layer has a thickness of 1 μm or less, wherein the protrusion has a plurality of micro-protrusions, the micro-protrusions are formed on the side surface other than the plateau of the protrusion, so as to improve the adhesion to an insulating resin substrate due to its increased surface area.
在一個實施例中,每單位面積(μm²)可以有80至2500個突出物。In one embodiment, there may be 80 to 2500 protrusions per unit area (μm²).
在一個實施例中,該金屬層可以具有0.20至0.80 μm的表面粗糙度(Rz)。In one embodiment, the metal layer may have a surface roughness (Rz) of 0.20 to 0.80 μm.
在一個實施例中,該金屬層可以具有110至165%的開發表面積比(developed surface area ratio, SDR)。In one embodiment, the metal layer may have a developed surface area ratio (SDR) of 110 to 165%.
在一個實施例中,除了該高台外的凸起之側表面可以具有0.05至0.3 μm的粗糙度(Ra)。In one embodiment, the side surface of the protrusions excluding the plateau may have a roughness (Ra) of 0.05 to 0.3 μm.
在一個實施例中,該凸起可以在其表面上形成複數個微突出物。In one embodiment, the protrusion may form a plurality of micro-protrusions on its surface.
在一個實施例中,該凸起的高度(b)與該凸起的底部長度(a)的比例可以是0.4:1至1.5:1(b:a)。In one embodiment, the ratio of the height (b) of the protrusion to the bottom length (a) of the protrusion may be 0.4:1 to 1.5:1 (b:a).
在一個實施例中,該高台的長度(c)與該凸起的底部長度(a)的比例可以是0.1:1至0.7:1(c/a)。In one embodiment, the ratio of the length of the plateau (c) to the length of the bottom of the protrusion (a) may be 0.1:1 to 0.7:1 (c/a).
在一個實施例中,該多角形截頂金字塔的形狀可以選自由五角形截頂金字塔、六角形截頂金字塔、七角形截頂金字塔及八角形截頂金字塔形狀所組成之群組。In one embodiment, the shape of the polygonal truncated pyramid can be selected from the group consisting of a pentagonal truncated pyramid, a hexagonal truncated pyramid, a heptagonal truncated pyramid, and an octagonal truncated pyramid.
在一個實施例中,該金屬層可以透過在一基材上直接電鍍或轉移形成在一載體上的一金屬箔來形成。In one embodiment, the metal layer can be formed by direct electroplating on a substrate or by transfer forming a metal foil on a carrier.
本發明也提供一種載體貼附金屬箔,其包括一載體、在該載體上形成的一釋放層以及在該釋放層上形成的一金屬層。The present invention also provides a carrier-attached metal foil, which includes a carrier, a release layer formed on the carrier, and a metal layer formed on the release layer.
本發明也提供一種基材,該金屬層的表面形態可以被轉移至該基材。The present invention also provides a substrate to which the surface morphology of the metal layer can be transferred.
有利效果 根據本發明在該金屬層的表面上形成該頂部平坦的突出物,使該金屬層具有對一絕緣樹脂基材的高黏附強度,並且能夠將高頻訊號傳輸的損失最小化。 該複數個突出物是在無電電鍍期間自然形成的,避免用於形成該金屬層上的不規則性之額外粗糙化需求,不同於習知技術。因此,根據本發明的金屬層可以能夠讓印刷電路板的製造具有高效率。 Advantageous Effects According to the present invention, the top flat protrusion is formed on the surface of the metal layer, so that the metal layer has high adhesion strength to an insulating resin substrate and can minimize the loss of high-frequency signal transmission. The plurality of protrusions are naturally formed during electroless plating, avoiding the need for additional roughening for forming irregularities on the metal layer, which is different from the conventional technology. Therefore, the metal layer according to the present invention can enable the manufacture of printed circuit boards to be efficient.
現在將詳細描述本發明的較佳實施例。在本發明的描述中,當認為相關技術可能不必要地模糊本發明的本質時,將省略它們的詳細解釋。如本文所使用的,單數形式的「一」、「一個」和「該」旨在也包括複數形式,除非上下文明確指示另有所指。在本發明中,應理解諸如「包括」或「具有」等的術語旨在指示揭示於說明書中的特徵、數字、步驟、操作、行動、組件、部分或其組合的存在,而不旨在排除可以存在或加入一個或多個其他特徵、數字、步驟、操作、行動、組件、部分或其組合的可能性,或可能被添加。本文所述方法的個別步驟可以以與明確描述的順序不同的順序執行。換句話說,個別步驟可以按照描述的相同順序,實質上同時或以相反的順序進行。The preferred embodiments of the present invention will now be described in detail. In the description of the present invention, when it is considered that the relevant technologies may unnecessarily obscure the essence of the present invention, their detailed explanation will be omitted. As used herein, the singular forms of "a", "an" and "the" are intended to also include plural forms, unless the context clearly indicates otherwise. In the present invention, it should be understood that terms such as "including" or "having" are intended to indicate the presence of features, numbers, steps, operations, actions, components, parts or combinations thereof disclosed in the specification, and are not intended to exclude the possibility that one or more other features, numbers, steps, operations, actions, components, parts or combinations thereof may exist or be added, or may be added. The individual steps of the method described herein may be performed in an order different from the order explicitly described. In other words, the individual steps may be performed in the same order as described, substantially simultaneously, or in reverse order.
本發明不限於所示出的實施例,並且可以在各種不同的形式中實施。相反地,揭示的實施例被提供以使得本揭示內容徹底而完整,並將本發明的範圍完全傳達給本發明所屬技術領域中具有通常知識者。在圖式中,元件的尺寸,諸如寬度和厚度,可以為了清晰而被誇大。圖式由觀察者的角度解釋。將理解,當參考一個元件為「在」另一個元件上時,它能夠直接在另一個元件上,或者也可以在它們之間存在一個或多個介入的元件。本發明所屬技術領域中具有通常知識者將理解,本發明可以在各種不同的形式中實施,而不偏離由附加的請求項所定義的發明之精神和範圍。相同的參考數字在整個圖式中表示實質上相同的元件。The present invention is not limited to the embodiments shown and may be implemented in a variety of different forms. On the contrary, the disclosed embodiments are provided to make the disclosure thorough and complete and to fully convey the scope of the present invention to those of ordinary skill in the art to which the present invention belongs. In the drawings, the dimensions of the elements, such as width and thickness, may be exaggerated for clarity. The drawings are interpreted from the perspective of the observer. It will be understood that when an element is referred to as "on" another element, it can be directly on the other element, or there may be one or more intervening elements between them. Those of ordinary skill in the art to which the present invention belongs will understand that the present invention may be implemented in a variety of different forms without departing from the spirit and scope of the invention as defined by the attached claims. The same reference numerals represent substantially the same elements throughout the drawings.
如本文所使用的,「和/或」涵蓋揭示的複數個相關項目的組合以及揭示的複數個相關項目中的任何項目。在本說明書中,「A或B」的描述意指「A」、「B」或「A和B」。As used herein, "and/or" covers the combination of multiple related items disclosed and any items in the multiple related items disclosed. In this specification, the description of "A or B" means "A", "B" or "A and B".
參考圖1,本發明的金屬層100包含複數個頂部平坦的突出物10。突出物10可以是從金屬層100的表面垂直向上凸起的金屬晶體顆粒。具體地,每個突出物10可以包括凸起11和高台12。1 , the metal layer 100 of the present invention includes a plurality of protrusions 10 with flat tops. The protrusions 10 may be metal crystal particles protruding vertically upward from the surface of the metal layer 100. Specifically, each protrusion 10 may include a protrusion 11 and a plateau 12.
突出物10的凸起11是從金屬層100的表面凸起的部分,並且可以具有截頂圓錐或是多角形截頂金字塔的形狀。具體地,凸起11具有帶有平坦平面(側表面)的截頂圓錐或是帶有成角度表面的多角形截頂金字塔形狀,如圖2所示。這種形狀能夠提升金屬層與絕緣樹脂基材的錨定力,使得金屬層100能夠與絕緣樹脂基材以高黏附強度結合。更具體地,凸起11可以具有至少一個多角形截頂金字塔形狀,該多角形截頂金字塔的形狀選自由五角形截頂金字塔、六角形截頂金字塔、七角形截頂金字塔及八角形截頂金字塔形狀所組成之群組。The protrusion 11 of the protrusion 10 is a portion protruding from the surface of the metal layer 100, and may have a truncated cone or a polygonal truncated pyramid shape. Specifically, the protrusion 11 has a truncated cone with a flat plane (side surface) or a polygonal truncated pyramid shape with an angled surface, as shown in FIG2. Such a shape can enhance the anchoring force of the metal layer and the insulating resin substrate, so that the metal layer 100 can be bonded to the insulating resin substrate with high adhesive strength. More specifically, the protrusion 11 may have at least one polygonal truncated pyramid shape, and the shape of the polygonal truncated pyramid is selected from the group consisting of a pentagonal truncated pyramid, a hexagonal truncated pyramid, a heptagonal truncated pyramid and an octagonal truncated pyramid.
該等凸起11中的每一個可以具有複數個微突出物11a,以由於其增加的表面積而提升對絕緣樹脂基材的黏附力。微突出物11a的形成使凸起11具有0.05至0.3 μm的表面粗糙度(Ra),具體為0.08至0.2 μm。在此,凸起11的表面粗糙度(Ra)定義為除了高台12以外的凸起11的側表面的粗糙度。Each of the protrusions 11 may have a plurality of micro-protrusions 11a to improve adhesion to the insulating resin substrate due to its increased surface area. The formation of the micro-protrusions 11a allows the protrusions 11 to have a surface roughness (Ra) of 0.05 to 0.3 μm, specifically 0.08 to 0.2 μm. Here, the surface roughness (Ra) of the protrusion 11 is defined as the roughness of the side surface of the protrusion 11 excluding the plateau 12.
同時,每個凸起11的高度(b)與凸起11的底部長度(a)的比例可以在0.4:1至1.5:1(b:a)的範圍內,具體為0.6:1至1.2:1(b:a)。當比例(b:a)在上述定義範圍內時,能夠提升金屬層100和絕緣樹脂基材之間的黏附力,並且能夠使高頻訊號傳輸的損失最小化。Meanwhile, the ratio of the height (b) of each protrusion 11 to the bottom length (a) of the protrusion 11 can be in the range of 0.4:1 to 1.5:1 (b:a), specifically 0.6:1 to 1.2:1 (b:a). When the ratio (b:a) is within the above-defined range, the adhesion between the metal layer 100 and the insulating resin substrate can be improved, and the loss of high-frequency signal transmission can be minimized.
突出物10的高台12是凸起11的上端的平坦表面。高台12可以是具有截頂圓錐或是多角形截頂金字塔形狀的凸起11的上表面。根據習知技術,顆粒從金屬層的表面尖銳或圓滑地凸起,以形成使金屬層表面高度粗糙的不規則性。不規則性的形成能夠提升與絕緣樹脂基材的黏附力,但會導致高頻訊號傳輸的損失。相比之下,形成突出物10頂部表面(頂端)的高台12使得本發明的金屬層100由於其平坦性而具有相對低的表面粗糙度。相對低的表面粗糙度使高頻訊號傳輸的損失最小化。具體地,高台12可以具有圓形、橢圓形或多角形的形狀。精細的不規則物可以被密集地形成以提供平坦的表面,這也能夠視為被涵蓋在高台12的範圍內。The plateau 12 of the protrusion 10 is a flat surface at the upper end of the protrusion 11. The plateau 12 may be the upper surface of the protrusion 11 having a truncated cone or a polygonal truncated pyramid shape. According to the known technology, particles protrude sharply or smoothly from the surface of the metal layer to form irregularities that make the surface of the metal layer highly rough. The formation of irregularities can enhance adhesion with the insulating resin substrate, but may result in loss of high-frequency signal transmission. In contrast, the plateau 12 forming the top surface (top) of the protrusion 10 enables the metal layer 100 of the present invention to have a relatively low surface roughness due to its flatness. The relatively low surface roughness minimizes the loss of high-frequency signal transmission. Specifically, the plateau 12 may have a circular, elliptical or polygonal shape. Fine irregularities may be densely formed to provide a flat surface, which can also be considered to be encompassed within the range of the plateau 12.
在該等突出物10的每一個中,高台12的長度(c)與凸起11的基底長度(a)的比例可以在0.1:1至0.7:1的範圍內,具體為0.2:1至0.6:1。當比例(c:a)在上述定義的範圍內時,能夠提升金屬箔100與絕緣樹脂基材之間的黏附力,並使高頻訊號傳輸的損失最小化。高台12的長度(c)指的是高台12的平面上之最大長度。In each of the protrusions 10, the ratio of the length (c) of the plateau 12 to the base length (a) of the protrusion 11 can be in the range of 0.1:1 to 0.7:1, specifically 0.2:1 to 0.6:1. When the ratio (c:a) is within the above-defined range, the adhesion between the metal foil 100 and the insulating resin substrate can be improved, and the loss of high-frequency signal transmission can be minimized. The length (c) of the plateau 12 refers to the maximum length on the plane of the plateau 12.
金屬層100的每單位面積(1 μm²)的突出物10的數量可以是80至2500個,考慮到金屬層100和絕緣樹脂基材之間的黏附力、高頻訊號的傳輸效率、金屬層100的電路線路解析度。如果每單位面積的突出物數量小於80個,突出物在尺寸上會增大並傾向於融合,結果為金屬層的表面積可能會減少,造成黏附強度降低。同時,如果每單位面積的突出物數量超過2500個,突出物在尺寸上會減小,結果為金屬層的表面積也可能同樣地減少,造成黏附強度降低。The number of protrusions 10 per unit area (1 μm²) of the metal layer 100 may be 80 to 2500, taking into account the adhesion between the metal layer 100 and the insulating resin substrate, the transmission efficiency of high-frequency signals, and the circuit line resolution of the metal layer 100. If the number of protrusions per unit area is less than 80, the protrusions will increase in size and tend to fuse, with the result that the surface area of the metal layer may decrease, resulting in a decrease in adhesion strength. At the same time, if the number of protrusions per unit area exceeds 2500, the protrusions will decrease in size, with the result that the surface area of the metal layer may also decrease, resulting in a decrease in adhesion strength.
突出物10可以透過無電電鍍形成。具體地,突出物10能夠透過無電電鍍形成金屬種子層來在金屬層100的表面上形成,之後在金屬種子層上連續生長晶體顆粒。根據習知技術,透過額外粗糙化金屬層來使不規則性形成。相比之下,在形成本發明的金屬層100的過程中,該複數個突出物10自然地形成粗糙表面。由此,避免額外的粗糙化需要,使得能夠讓金屬層100的形成和/或印刷電路板的製造具有高效率。另外,無電電鍍使金屬層100比電鍍的厚度更小且具有更多孔。The protrusions 10 can be formed by electroless plating. Specifically, the protrusions 10 can be formed on the surface of the metal layer 100 by forming a metal seed layer by electroless plating, and then continuously growing crystalline grains on the metal seed layer. According to the known technology, irregularities are formed by additionally roughening the metal layer. In contrast, in the process of forming the metal layer 100 of the present invention, the plurality of protrusions 10 naturally form a rough surface. Thus, the need for additional roughening is avoided, enabling the formation of the metal layer 100 and/or the manufacture of the printed circuit board to be efficient. In addition, electroless plating makes the metal layer 100 thinner and more porous than electroplating.
用於形成金屬層100的無電鍍液的組成沒有特定限制並且可以包括金屬離子來源和含氮化合物。The composition of the electroless plating solution used to form the metal layer 100 is not particularly limited and may include a metal ion source and a nitrogen-containing compound.
金屬離子來源具體地可以為銅離子來源,其選自由硫酸銅、氯化銅、硝酸銅、氫氧化銅、胺基磺酸銅及其混合物。金屬離子來源可以以0.5至10 g/L的濃度存在,具體地為1至8 g/L。The metal ion source can be specifically a copper ion source selected from copper sulfate, copper chloride, copper nitrate, copper hydroxide, copper sulfamate and mixtures thereof. The metal ion source can be present in a concentration of 0.5 to 10 g/L, specifically 1 to 8 g/L.
含氮化合物使金屬離子擴散以形成由金屬離子來源形成的金屬種子層表面上的複數個突出物10。具體地,含氮化合物可以選自由嘌呤、腺嘌呤、鳥糞嘌呤、次黃嘌呤、黃嘌呤、嗒嗪、甲基哌啶、1,2-二-(2-吡啶基)乙烯、1,2-二-(吡啶基)乙烯、2,2'-二吡啶基胺、2,2'-雙吡啶基、2,2'-雙嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-呋喃酮、N,N,N',N'-四乙烯二胺、1,8-萘啶、1,6-萘啶、三吡啶及其混合物所組成之群組。含氮化合物可以以0.01至10 g/L的濃度存在,具體為0.05至1 g/L。The nitrogen-containing compound diffuses metal ions to form a plurality of protrusions 10 on the surface of the metal seed layer formed by the metal ion source. Specifically, the nitrogen-containing compound can be selected from the group consisting of purine, adenine, guanine, hypoxanthine, xanthine, pyridazine, methyl piperidine, 1,2-di-(2-pyridyl)ethylene, 1,2-di-(pyridyl)ethylene, 2,2'-dipyridylamine, 2,2'-bipyridyl, 2,2'-bipyrimidine, 6,6'-dimethyl-2,2'-bipyridyl, di-2-furanone, N,N,N',N'-tetraethylenediamine, 1,8-naphthyridine, 1,6-naphthyridine, tripyridine and mixtures thereof. The nitrogen-containing compound may be present in a concentration of 0.01 to 10 g/L, specifically 0.05 to 1 g/L.
無電鍍液可以進一步包括一種或多種添加劑,其選自由螯合劑、pH調整劑及還原劑所組成之群組。The electroless plating solution may further include one or more additives selected from the group consisting of a chelating agent, a pH adjuster and a reducing agent.
具體地,螯合劑可以選自由酒石酸、檸檬酸、醋酸、蘋果酸、丙二酸、抗壞血酸、草酸、乳酸、琥珀酸、酒石酸鉀鈉、酒石酸二鉀、2,4-咪唑啶二酮、1-甲基2,4-咪唑啶二酮、1,3-二甲基2,4-咪唑啶二酮、5,5-二甲基2,4-咪唑啶二酮、氮基三乙酸、三乙醇胺、乙二胺四乙酸、乙二胺四乙酸四鈉、N-羥基乙二胺三乙酸、五羥基丙基二乙烯三胺及其混合物所組成之群組。螯合劑可以以0.5至150 g/L的濃度存在,具體為20至100 g/L。Specifically, the chelating agent can be selected from the group consisting of tartaric acid, citric acid, acetic acid, apple acid, malonic acid, ascorbic acid, oxalic acid, lactic acid, succinic acid, potassium sodium tartrate, dipotassium tartrate, 2,4-imidazolidinone, 1-methyl 2,4-imidazolidinone, 1,3-dimethyl 2,4-imidazolidinone, 5,5-dimethyl 2,4-imidazolidinone, nitrilotriacetic acid, triethanolamine, ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, N-hydroxyethylenediaminetriacetic acid, pentahydroxypropyldiethylenetriamine and mixtures thereof. The chelating agent can be present in a concentration of 0.5 to 150 g/L, specifically 20 to 100 g/L.
具體地,pH調整劑可以選自由氫氧化鈉、氫氧化鉀、氫氧化鋰及其混合物所組成之群組。pH調整劑能夠調整無電鍍液的pH值至8或更高,具體為10至14,更具體為11至13.5。Specifically, the pH adjuster can be selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof. The pH adjuster can adjust the pH value of the electroless plating solution to 8 or higher, specifically 10 to 14, more specifically 11 to 13.5.
具體地,還原劑可以選自由甲醛、次磷酸鈉、羥基甲烷亞磺酸鈉、乙醛酸、硼氫化物、二甲基胺硼烷及其混合物所組成之群組。還原劑可以以1至20 g/L的濃度存在,具體為5至20 g/L。Specifically, the reducing agent can be selected from the group consisting of formaldehyde, sodium hypophosphite, sodium hydroxymethanesulfinate, glyoxylic acid, borohydride, dimethylamine borane and mixtures thereof. The reducing agent can be present in a concentration of 1 to 20 g/L, specifically 5 to 20 g/L.
無電電鍍形成金屬層100的條件可以依據金屬層100的厚度進行適當調整。具體地,無電電鍍溫度可以為20至60℃,具體為30至40℃並且無電電鍍時間可以為2至30分鐘,具體為5至20分鐘。The conditions for forming the metal layer 100 by electroless plating can be appropriately adjusted according to the thickness of the metal layer 100. Specifically, the electroless plating temperature can be 20 to 60° C., specifically 30 to 40° C., and the electroless plating time can be 2 to 30 minutes, specifically 5 to 20 minutes.
由無電電鍍形成的金屬層100的厚度可以為5 μm或更小,具體為0.1至1 μm。金屬層100的組份沒有特定限制,可以是任何能夠形成印刷電路板的電路層之已知金屬。具體地,金屬可以選自由銅、銀、金、鎳、鋁及其混合物所組成之群組。The thickness of the metal layer 100 formed by electroless plating can be 5 μm or less, specifically 0.1 to 1 μm. The composition of the metal layer 100 is not particularly limited, and can be any known metal that can form a circuit layer of a printed circuit board. Specifically, the metal can be selected from the group consisting of copper, silver, gold, nickel, aluminum, and mixtures thereof.
金屬層可以有0.20至0.80 μm範圍內的表面粗糙度(Rz)。突出物的形成使金屬層具有上述定義範圍內的適當表面粗糙度(Rz),由此確保對絕緣樹脂基材之顯著改進的黏附力。金屬層的Rz低於0.2 μm可能會降低金屬層的黏附強度。同時,超過0.8 μm的金屬層的Rz,即過大的突出物,同樣可能導致金屬層的黏附強度降低。The metal layer may have a surface roughness (Rz) in the range of 0.20 to 0.80 μm. The formation of the protrusions enables the metal layer to have an appropriate surface roughness (Rz) in the above-defined range, thereby ensuring significantly improved adhesion to the insulating resin substrate. The Rz of the metal layer below 0.2 μm may reduce the adhesion strength of the metal layer. At the same time, the Rz of the metal layer exceeding 0.8 μm, that is, excessively large protrusions, may also lead to reduced adhesion strength of the metal layer.
該金屬層可以具有110%至165%的開發表面積比(SDR)。開發表面積比被定義為從上方看實際表面積與單位面積的比例,開發表面積比是代表每單位面積的表面積增加之數值。增加的表面積會帶來基材將與其結合的金屬層之面積增加,這一般能夠改進金屬層與基材的黏附力。為了嘗試將金屬層的表面積增加到高於預定水準,金屬層中形成了空腔或在金屬層上形成了非均勻大小的突出物。然而,此嘗試同樣導致金屬層的黏附強度降低。如果SDR小於110%,金屬層之不顯著增加的表面積可能不會帶來黏附強度的顯著提升。同時,如果SDR超過165%,可能會因上述原因導致黏附強度的降低。The metal layer may have a developed surface area ratio (SDR) of 110% to 165%. The developed surface area ratio is defined as the ratio of the actual surface area viewed from above to the unit area, and the developed surface area ratio is a numerical value representing the increase in surface area per unit area. The increased surface area results in an increase in the area of the metal layer to which the substrate will bond, which generally improves the adhesion of the metal layer to the substrate. In an attempt to increase the surface area of the metal layer above a predetermined level, cavities are formed in the metal layer or protrusions of uneven sizes are formed on the metal layer. However, this attempt also results in a decrease in the adhesion strength of the metal layer. If the SDR is less than 110%, a not-significantly increased surface area of the metal layer may not result in a significant improvement in adhesion strength. At the same time, if the SDR exceeds 165%, the adhesion strength may be reduced due to the above reasons.
本發明也提供了一種包括金屬層的載體貼附金屬箔。具體地,載體貼附金屬箔包括載體、釋放層及金屬層,其中該金屬層與上述的金屬層相同。下面將詳細描述載體貼附金屬箔。The present invention also provides a carrier-attached metal foil including a metal layer. Specifically, the carrier-attached metal foil includes a carrier, a release layer and a metal layer, wherein the metal layer is the same as the above-mentioned metal layer. The carrier-attached metal foil will be described in detail below.
根據本發明的載體貼附金屬箔的載體是用來避免在運輸或使用載體貼附金屬箔期間金屬層變形。載體可以由諸如銅或鋁的金屬製成。替代地,載體可以由諸如聚對苯二甲酸乙二酯(polyethylene terephthalate, PET)、聚苯硫醚(polyphenylene sulfide, PPS)或鐵氟龍的聚合物製成。載體的厚度可以具體為10至50 μm。The carrier of the carrier-attached metal foil according to the present invention is used to avoid deformation of the metal layer during transportation or use of the carrier-attached metal foil. The carrier can be made of metals such as copper or aluminum. Alternatively, the carrier can be made of polymers such as polyethylene terephthalate (PET), polyphenylene sulfide (PPS) or Teflon. The thickness of the carrier can be specifically 10 to 50 μm.
載體貼附金屬箔的釋放層設計被用於容易地從與絕緣樹脂基材結合的載體貼附金屬箔中移除載體。釋放層可以具有單層或多層結構。具體地,釋放層可以具有單層結構,其含有作為有機材料的含氮環狀化合物,並且含有選自由鎳、鉬、鈷、磷、錳和鐵所組成之群組的金屬。亦即,單層是有機/無機複合層。替代地,釋放層可以具有多層結構,其中有機層與合金層結合,有機層由含氮環狀化合物組成,合金層包括一種或多種金屬,其選自由鎳、鉬、鈷、磷、錳和鐵所組成之群組。釋放層可以具有30 nm至1 μm的厚度。The release layer design of the carrier-attached metal foil is used to easily remove the carrier from the carrier-attached metal foil bonded to the insulating resin substrate. The release layer can have a single-layer or multi-layer structure. Specifically, the release layer can have a single-layer structure, which contains a nitrogen-containing cyclic compound as an organic material and contains a metal selected from the group consisting of nickel, molybdenum, cobalt, phosphorus, manganese and iron. That is, the single layer is an organic/inorganic composite layer. Alternatively, the release layer can have a multi-layer structure, in which an organic layer is bonded to an alloy layer, the organic layer is composed of a nitrogen-containing cyclic compound, and the alloy layer includes one or more metals selected from the group consisting of nickel, molybdenum, cobalt, phosphorus, manganese and iron. The release layer may have a thickness of 30 nm to 1 μm.
載體貼附金屬箔的金屬層與上述金屬層相同,由此省略了詳細描述。The metal layer of the carrier-attached metal foil is the same as the above-mentioned metal layer, so the detailed description is omitted.
本發明的載體貼附金屬箔可以進一步包括在金屬層上形成的電解金屬層,以提升金屬層的機械強度和導電性。電解金屬層可以由與金屬層相同或不同的組分組成。The carrier-attached metal foil of the present invention may further include an electrolytic metal layer formed on the metal layer to enhance the mechanical strength and electrical conductivity of the metal layer. The electrolytic metal layer may be composed of the same or different components as the metal layer.
本發明的載體貼附金屬箔可以進一步包括在金屬層上形成的防鏽層,以保護金屬層不生鏽的。例如,防鏽層可以包括鋅或鉻。The carrier-attached metal foil of the present invention may further include a rust-proof layer formed on the metal layer to protect the metal layer from rusting. For example, the rust-proof layer may include zinc or chromium.
本發明的載體貼附金屬箔可以進一步包括在載體和釋放層的合金層之間形成的擴散屏障層,用以改進其性能。例如,擴散屏障層可以包括鎳或磷。The carrier-attached metal foil of the present invention may further include a diffusion barrier layer formed between the carrier and the alloy layer of the release layer to improve its performance. For example, the diffusion barrier layer may include nickel or phosphorus.
本發明的載體貼附金屬箔可以進一步包括在釋放層的有機層和金屬層之間形成的氧化屏障層。例如,氧化屏障層可以包括鎳或磷。The carrier-attached metal foil of the present invention may further include an oxidation barrier layer formed between the organic layer of the release layer and the metal layer. For example, the oxidation barrier layer may include nickel or phosphorus.
本發明也提供使用金屬層製造的印刷電路板。具體地,本發明的印刷電路板包括金屬電路層和絕緣樹脂層。金屬電路層是透過金屬層在基材上直接電鍍或將金屬箔轉移到基材上形成金屬層而形成的,這將在下面描述。The present invention also provides a printed circuit board manufactured using a metal layer. Specifically, the printed circuit board of the present invention includes a metal circuit layer and an insulating resin layer. The metal circuit layer is formed by directly electroplating the metal layer on a substrate or transferring a metal foil to a substrate to form a metal layer, which will be described below.
印刷電路板的金屬電路層是形成電路線路的層。金屬電路層可以透過在基材上直接無電電鍍金屬層來形成,如上所述。可以透過本領域已知的適合方法來形成金屬層和使用金屬層的金屬電路。The metal circuit layer of the printed circuit board is a layer that forms a circuit line. The metal circuit layer can be formed by electroless plating of the metal layer directly on the substrate, as described above. The metal layer and the metal circuit using the metal layer can be formed by a suitable method known in the art.
金屬電路層是透過在金屬箔上形成電路線路而獲得的。金屬箔確保了印刷電路板的小型化和高解析度。具體地,本發明的印刷電路板是透過結合絕緣樹脂基材和金屬箔來形成層壓板,並且蝕刻層壓板在金屬箔上形成電路線路而被製造。用於金屬箔的金屬層與具有高黏附強度的絕緣樹脂基材結合,並且金屬層具有相對較小的厚度,能夠使得在其上形成精細和高解析度的電路線路。另外,形成在金屬箔上的電路線路具有對絕緣樹脂基材的高黏附強度。The metal circuit layer is obtained by forming a circuit line on a metal foil. The metal foil ensures miniaturization and high resolution of the printed circuit board. Specifically, the printed circuit board of the present invention is manufactured by forming a laminate by combining an insulating resin substrate and a metal foil, and etching the laminate to form a circuit line on the metal foil. The metal layer for the metal foil is combined with an insulating resin substrate having a high adhesion strength, and the metal layer has a relatively small thickness, enabling a fine and high-resolution circuit line to be formed thereon. In addition, the circuit line formed on the metal foil has a high adhesion strength to the insulating resin substrate.
形成電路線路的方法沒有特定限制。例如,電路線路可以透過減成製程、加成製程、全加成製程、半加成製程或修改的半加成製程來形成。The method of forming the circuit line is not particularly limited. For example, the circuit line can be formed by a subtractive process, an additive process, a full additive process, a semi-additive process, or a modified semi-additive process.
印刷電路板的絕緣樹脂層是在金屬電路層上形成的絕緣層。絕緣樹脂層可以是任何適合的、本領域習知的絕緣樹脂基材。具體地,絕緣樹脂層可以是具有一結構的基材,在該結構中習知的樹脂被浸入無機或有機纖維中。例如,樹脂基材可以是預浸體。The insulating resin layer of the printed circuit board is an insulating layer formed on the metal circuit layer. The insulating resin layer can be any suitable insulating resin substrate known in the art. Specifically, the insulating resin layer can be a substrate having a structure in which a known resin is impregnated in an inorganic or organic fiber. For example, the resin substrate can be a prepreg.
本發明的印刷電路板可以透過使用絕緣樹脂基材或透過不使用絕緣樹脂基材的無核製程來製造。The printed circuit board of the present invention can be manufactured by using an insulating resin substrate or by a coreless process without using an insulating resin substrate.
透過轉移或電鍍貼附到絕緣樹脂基材的金屬層可以具有250到800 g f/cm的黏附強度。傳統的金屬層包括不均勻的突出物或具有不適合的物理特性,這解釋了它們的低黏附強度。具體地,傳統的金屬層已知具有高達250 gf/cm的黏附強度。相比之下,本發明的金屬層因為具有適合的物理特性並且包含均勻大小的突出物,因此具有比傳統金屬層更高的黏附強度。 A metal layer attached to an insulating resin substrate by transfer or electroplating can have an adhesion strength of 250 to 800 gf /cm. Conventional metal layers include uneven protrusions or have inappropriate physical properties, which explains their low adhesion strength. Specifically, conventional metal layers are known to have an adhesion strength of up to 250 gf/cm. In contrast, the metal layer of the present invention has a higher adhesion strength than conventional metal layers because it has suitable physical properties and includes protrusions of uniform size.
本發明也提供了一種基材,金屬層的表面形態可以被轉移至該基材。The present invention also provides a substrate to which the surface morphology of the metal layer can be transferred.
在使用前,金屬層可以被轉移到絕緣基材上。該絕緣基材與上述相同。在此情況下,在將突出物的形狀轉移到基材上後,可以移除金屬層。由於凸起在基材上形成相同形狀的凹陷,因此轉移到基材上的形狀具有與金屬層相似的粗糙度(Rz)和SDR值。轉移後金屬層可以被簡單地剝離。替代地,由於突出物的存在使金屬層具有高黏附強度,因此轉移後金屬層可以透過蝕刻被移除。Before use, the metal layer can be transferred to an insulating substrate. The insulating substrate is the same as described above. In this case, the metal layer can be removed after the shape of the protrusion is transferred to the substrate. Since the protrusion forms a depression of the same shape on the substrate, the shape transferred to the substrate has a roughness (Rz) and SDR value similar to that of the metal layer. The metal layer can be simply peeled off after transfer. Alternatively, since the presence of the protrusion gives the metal layer a high adhesion strength, the metal layer can be removed by etching after transfer.
在傳統金屬層的表面形態轉移後,需要大量的蝕刻,因為金屬層上形成的突出物形狀不均勻。由此,增加金屬層表面形態被轉移到其上之基材的黏附強度存在限制。相比之下,由於根據本發明的金屬層的突出物大小均勻,因此金屬層能夠透過最小量的蝕刻從基材表面移除,由此可能使基材具有高黏附強度。After the surface morphology of the conventional metal layer is transferred, a large amount of etching is required because the protrusions formed on the metal layer are not uniform in shape. Thus, there is a limit to increasing the adhesion strength of the substrate to which the surface morphology of the metal layer is transferred. In contrast, since the protrusions of the metal layer according to the present invention are uniform in size, the metal layer can be removed from the substrate surface by a minimum amount of etching, thereby making it possible to make the substrate have high adhesion strength.
詳細而言,如果金屬層上形成的突出物大小不均勻,則應進行蝕刻,直到參考中最大的突出物被移除。然而,在此情況下,由於移除最大突出物前已蝕刻掉較小的突出物,因此在已從其上移除較小突出物的金屬層部分上繼續蝕刻的時間比必要的時間長,造成低表面粗糙度。亦即,如果突出物大小不均勻,則即使在完成基材上的表面形態轉移後,也可能難以獲得高於預定水準的表面粗糙度,帶來黏附強度的降低。In detail, if the protrusions formed on the metal layer are uneven in size, etching should be performed until the largest protrusion in the reference is removed. However, in this case, since the smaller protrusions are etched before the largest protrusion is removed, etching is continued for a longer time than necessary on the portion of the metal layer from which the smaller protrusions have been removed, resulting in low surface roughness. That is, if the protrusions are uneven in size, it may be difficult to obtain a surface roughness higher than a predetermined level even after the surface morphology transfer on the substrate is completed, resulting in a decrease in adhesion strength.
相比之下,由於本發明的金屬層的凸起大小恆定,如圖3所示,它們幾乎可以均勻地被蝕刻掉。因此,可以防止凸起被過度蝕刻,從而最大限度地減少表面粗糙度的減少。因此,本發明的基材比先前發明的基材具有更高的黏附強度。In contrast, since the protrusions of the metal layer of the present invention are of constant size, as shown in FIG3 , they can be etched away almost uniformly. Therefore, the protrusions can be prevented from being overetched, thereby minimizing the reduction in surface roughness. Therefore, the substrate of the present invention has a higher adhesion strength than the substrate of the previous invention.
發明模式 本發明將參考以下示例更具體地解釋。然而,這些示例僅提供用於說明用途,並不旨在限制本發明的範圍。本發明所屬技術領域中具有通常知識者將理解,可以在不脫離本發明的範圍和精神的情況下進行各種修改和變化。 Invention Mode The present invention will be explained more specifically with reference to the following examples. However, these examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. A person having ordinary knowledge in the technical field to which the present invention belongs will understand that various modifications and changes can be made without departing from the scope and spirit of the present invention.
[示例1-27] 銅(Cu)箔載體被結合到釋放層(由鎳和鉬組成的合金層+由巰基苯並***鈉組成的有機層)以製備層壓板。該層壓板在無電電鍍浴中進行無電電鍍以在釋放層上形成金屬層(銅層)。用於無電電鍍的無電鍍液含有CuSO 4·5H 2O作為金屬離子來源(A),鳥糞嘌呤作為含氮化合物(B),酒石酸鉀鈉作為螯合劑(C),NaOH作為pH調節劑(D),並且甲醛作為還原劑(E)。金屬離子源、含氮化合物、螯合劑、pH調節劑及還原劑的濃度以及無電電鍍條件被調整如表1所示,以形成金屬箔。測量了金屬箔中的突出物的大小和數量。在表1中,所有的濃度都以g/L表示。 [Example 1-27] A copper (Cu) foil carrier is bonded to a release layer (alloy layer composed of nickel and molybdenum + organic layer composed of sodium nitrobenzotriazole) to prepare a laminate. The laminate is electrolessly plated in an electroless plating bath to form a metal layer (copper layer) on the release layer. The electroless plating solution used for electroless plating contains CuSO 4 ·5H 2 O as a metal ion source (A), guanosine as a nitrogen-containing compound (B), potassium sodium tartrate as a chelating agent (C), NaOH as a pH adjuster (D), and formaldehyde as a reducing agent (E). The concentrations of the metal ion source, nitrogen-containing compound, chelating agent, pH adjuster and reducing agent and the electroless plating conditions were adjusted as shown in Table 1 to form the metal foil. The size and number of protrusions in the metal foil were measured. In Table 1, all concentrations are expressed in g/L.
[表1]
比較例1 金屬層(銅層)以與示例4相同的方式形成,除了在含有作為金屬離子來源的8-15 g/L的CuSO 4·5H 2O和NiSO 4·6H 2O、作為含氮化合物的0.5-0.8 g/L的2,2-雙吡啶、作為螯合劑的60-80 g/L的酒石酸鉀鈉以及作為還原劑的28%甲醛之無電鍍液中進行無電電鍍,在34℃下反應20分鐘。 Comparative Example 1 A metal layer (copper layer) was formed in the same manner as in Example 4, except that electroless plating was performed in an electroless plating solution containing 8-15 g/L of CuSO 4 ·5H 2 O and NiSO 4 ·6H 2 O as metal ion sources, 0.5-0.8 g/L of 2,2-bipyridine as a nitrogen-containing compound, 60-80 g/L of sodium potassium tartrate as a chelating agent, and 28% formaldehyde as a reducing agent, at 34° C. for 20 minutes.
測試例1 示例1和比較例1中形成的金屬層的表面和橫截面被觀察,以比較金屬箔中形成之突出物的形狀。 Test Example 1 The surface and cross section of the metal layer formed in Example 1 and Comparative Example 1 were observed to compare the shapes of the protrusions formed in the metal foil.
以掃描電子顯微鏡(scanning electron microscope, SEM)和離子束橫截面拋光機(ion beam cross section polisher, CP)分析金屬層的表面和橫截面。結果示出於圖3中。The surface and cross section of the metal layer were analyzed using a scanning electron microscope (SEM) and an ion beam cross section polisher (CP). The results are shown in Figure 3.
參考圖3,示例1的創新金屬箔具有複數個頂部平坦的表面突出物,而比較例1的金屬箔具有複數個頂部尖銳的表面突出物。3 , the innovative metal foil of Example 1 has a plurality of surface protrusions with flat tops, while the metal foil of Comparative Example 1 has a plurality of surface protrusions with sharp tops.
結論為,使用與示例1中使用的相同組份的鍍液能夠使頂部平坦的突出物形成。It was concluded that the use of a plating solution having the same composition as that used in Example 1 enabled the formation of protrusions having flat tops.
測試例2 示例1-27中形成的金屬箔的突出物之大小及Rz、表面粗糙度和SDR值測量如下。 Test Example 2 The size of the protrusions of the metal foil formed in Example 1-27, as well as the Rz, surface roughness, and SDR values were measured as follows.
使用場發射掃描式電子顯微鏡(FE-SEM,型號SU-8010,日立)以50,000×的放大倍數觀察每個金屬箔的表面並測量單位面積的突出物大小。The surface of each metal foil was observed using a field emission scanning electron microscope (FE-SEM, model SU-8010, Hitachi) at a magnification of 50,000× and the protrusion size per unit area was measured.
使用原子力顯微鏡(AFM,型號多模式IVa,布魯克)在10 μm的掃描大小和0.5 Hz的掃描速率下測量每個金屬層的10點平均表面粗糙度(Rz)。The 10-point average surface roughness (Rz) of each metal layer was measured using an atomic force microscope (AFM, model Multimode IVa, Brooke) at a scan size of 10 μm and a scan rate of 0.5 Hz.
使用原子力顯微鏡(AFM,型號多模式IVa,布魯克)在1 μm的掃描大小和0.5 Hz的掃描速率下測量凸起之側表面的粗糙度(Ra)。The roughness (Ra) of the protrusion side surface was measured using an atomic force microscope (AFM, model Multimode IVa, Brooke) at a scan size of 1 μm and a scan rate of 0.5 Hz.
使用原子力顯微鏡(AFM,型號多模式IVa,布魯克)在10 μm的掃描大小和0.5 Hz的掃描速率下測量每個金屬層的表面積,以確定金屬層的SDR。The surface area of each metal layer was measured using an atomic force microscope (AFM, model Multimode IVa, Brook) at a scan size of 10 μm and a scan rate of 0.5 Hz to determine the SDR of the metal layer.
[表2]
從表2的結果能夠看出,示例4、10、17和24中所應用的條件最有效地增加金屬層的表面積。另外,示例4中形成的金屬層之突出物的數量以及金屬層的Rz和Ra值也被發現是適當的。It can be seen from the results in Table 2 that the conditions applied in Examples 4, 10, 17 and 24 were most effective in increasing the surface area of the metal layer. In addition, the number of protrusions of the metal layer formed in Example 4 and the Rz and Ra values of the metal layer were also found to be appropriate.
觀察到在示例1-7中形成的金屬層之物理性質隨著金屬離子來源濃度的變化而改變。當金屬離子來源的濃度為低時,突出物的形成不平滑。同時,當金屬離子來源的濃度超過預定水準時,金屬離子來源對金屬層的表面積之提升效果不顯著。這些結果似乎是由於金屬突出物的生長和融合,證明當金屬離子來源的濃度超過預定水準時,金屬層的Rz值會減小。It was observed that the physical properties of the metal layers formed in Examples 1-7 changed as the concentration of the metal ion source changed. When the concentration of the metal ion source was low, the protrusions were not formed smoothly. Meanwhile, when the concentration of the metal ion source exceeded a predetermined level, the metal ion source had an insignificant effect on increasing the surface area of the metal layer. These results appear to be due to the growth and fusion of the metal protrusions, demonstrating that when the concentration of the metal ion source exceeded a predetermined level, the Rz value of the metal layer decreased.
觀察到在示例8-14中形成的金屬層之物理性質隨著含氮化合物濃度的變化而改變。當含氮化合物的濃度低於預定水準時,突出物的形成不平滑(示例8)。同時,當含氮化合物的濃度超過預定水準時,凸起的側表面之粗糙度不足夠高(示例13-14)。這些結果的結論為,使用超過預定水準的濃度之含氮化合物會導致突出物形成不足和金屬層的物理性質不佳。It was observed that the physical properties of the metal layers formed in Examples 8-14 changed as the concentration of the nitrogen-containing compound changed. When the concentration of the nitrogen-containing compound was lower than a predetermined level, the protrusions were not formed smoothly (Example 8). Meanwhile, when the concentration of the nitrogen-containing compound exceeded the predetermined level, the roughness of the side surface of the protrusions was not high enough (Examples 13-14). These results lead to the conclusion that the use of a nitrogen-containing compound at a concentration exceeding the predetermined level results in insufficient protrusion formation and poor physical properties of the metal layer.
研究在示例15-20中形成的金屬層之物理性質中溫度依賴差異。當溫度為低時,突出物不容易形成和生長。同時,當在過高的溫度下進行反應時,觀察到突出物的過度生長和融合。具體地,在高溫下側向突出物的生長和融合導致高Ra值,但不能有效提升金屬層的表面積。The temperature-dependent differences in the physical properties of the metal layers formed in Examples 15-20 were studied. When the temperature was low, the protrusions were not easily formed and grown. Meanwhile, when the reaction was performed at an excessively high temperature, excessive growth and fusion of the protrusions were observed. Specifically, the growth and fusion of lateral protrusions at high temperatures resulted in high Ra values, but the surface area of the metal layer could not be effectively increased.
研究在示例21-27中形成的金屬層之物理性質中反應時間依賴差異。隨著反應時間的增加,大量的突出物生長和融合。然而,在反應時間提升到超過預定水準之後,突出物傾向融合,造成它們的數量減少。總而言之,超過預定水準的反應時間會減損其對金屬層的表面積之提升效果。隨著反應時間的增加,側向突出物也會融合。總而言之,只有當反應時間低於預定水準時,金屬層的表面積才會有效提升。The reaction time-dependent differences in the physical properties of the metal layers formed in Examples 21-27 were studied. As the reaction time increased, a large number of protrusions grew and fused. However, after the reaction time was increased to exceed a predetermined level, the protrusions tended to fuse, causing their number to decrease. In summary, a reaction time exceeding a predetermined level would reduce its effect on increasing the surface area of the metal layer. As the reaction time increased, the lateral protrusions also fused. In summary, the surface area of the metal layer would be effectively increased only when the reaction time was lower than a predetermined level.
[示例28-44][Example 28-44]
進行電鍍以形成具有表3中示出之突出物數量和Rz和Ra值的金屬層,以研究突出物數量以及金屬層的Rz和Ra值對金屬層的黏附強度和高頻訊號傳輸性能的影響。突出物以與示例4相同的方式形成,除了反應時間和含氮化合物的濃度被改變。Electroplating was performed to form a metal layer having the number of protrusions and the Rz and Ra values shown in Table 3 to study the effects of the number of protrusions and the Rz and Ra values of the metal layer on the adhesion strength and high-frequency signal transmission performance of the metal layer. The protrusions were formed in the same manner as in Example 4, except that the reaction time and the concentration of the nitrogen-containing compound were changed.
[表3]
測試例3Test Example 3
進行以下程序以確定在示例28-44中形成的金屬層的物理性質和高頻訊號傳輸性能。The following procedures were performed to determine the physical properties and high frequency signal transmission performance of the metal layers formed in Examples 28-44.
將SUS板、牛皮紙、釋放膜、絕緣樹脂基材(DS-7409HG)、示例1-7和比較例1中形成的每一個金屬層(包括釋放層)、牛皮紙及SUS板以此順序進行層壓,並在3.5 MPa的壓力和200℃的溫度下進行100分鐘的真空壓縮以製備層壓板。透過釋放層去除層壓板中的牛皮紙和SUS板後,透過IPC-TM-650測試方法(BMSP-90P剝離測試機,測試速度:50 mm/分,測試速度:90°)來評估金屬箔和絕緣樹脂基材之間的剝離強度。The SUS plate, kraft paper, release film, insulating resin substrate (DS-7409HG), each metal layer (including the release layer) formed in Examples 1 to 7 and Comparative Example 1, kraft paper, and SUS plate were laminated in this order and vacuum compressed at a pressure of 3.5 MPa and a temperature of 200° C. for 100 minutes to prepare a laminate. After the kraft paper and SUS plate in the laminate were removed through the release layer, the peel strength between the metal foil and the insulating resin substrate was evaluated by the IPC-TM-650 test method (BMSP-90P peel tester, test speed: 50 mm/min, test speed: 90°).
將銅箔(18 μm厚)、絕緣樹脂基材(DS-7402,50 μm)及示例1-7和比較例1中形成的每一個金屬層以此順序進行層壓,並透過mSAP在金屬箔上形成線材(寬度:40 μm,長度:10 cm)。在形成線材的金屬箔上層壓絕緣樹脂基材(DS-7402)和銅箔,並加工通孔以製造印刷電路板。使用PNA N5225A (KEYSIGHT)測量印刷電路板的高頻訊號傳輸性能。在10 MHz至40 GHz處測量S21參數(dB/cm)。結果示出於表4中。Copper foil (18 μm thick), insulating resin substrate (DS-7402, 50 μm), and each metal layer formed in Examples 1-7 and Comparative Example 1 were laminated in this order, and wires (width: 40 μm, length: 10 cm) were formed on the metal foil by mSAP. An insulating resin substrate (DS-7402) and copper foil were laminated on the metal foil forming the wire, and through holes were processed to manufacture a printed circuit board. The high-frequency signal transmission performance of the printed circuit board was measured using PNA N5225A (KEYSIGHT). The S21 parameter (dB/cm) was measured at 10 MHz to 40 GHz. The results are shown in Table 4.
對比較例1進行相同測試以確定沒有表面高台的金屬層的效果。The same test was performed on Comparative Example 1 to determine the effect of the metal layer without the surface plateau.
[表4]
表面上的平坦區域的數量隨著突出物的數量減少而增加(示例28-33),造成高頻訊號傳輸性能提高。然而,當突出物的數量低於預定水準(示例28和29)時,金屬層的黏附強度降低。同時,當突出物的數量超過預定水準時,沒有呈現突出物的融合,造成頂部平坦區域的數量減少,造成黏附強度和訊號傳輸性能降低。The amount of flat areas on the surface increases as the number of protrusions decreases (Examples 28-33), resulting in improved high-frequency signal transmission performance. However, when the number of protrusions is less than a predetermined level (Examples 28 and 29), the adhesion strength of the metal layer decreases. Meanwhile, when the number of protrusions exceeds a predetermined level, no fusion of the protrusions occurs, resulting in a decrease in the amount of top flat areas, resulting in decreased adhesion strength and signal transmission performance.
對於具有相似突出物數量之示例34-38的金屬層,黏附強度隨Rz的減小而降低。增加的Rz導致高黏附強度但不佳的訊號傳輸性能。For the metal layers of Examples 34-38 with similar protrusion numbers, the adhesion strength decreases as Rz decreases. Increasing Rz results in high adhesion strength but poor signal transmission performance.
當Ra低時(示例39),黏附強度降低但訊號傳輸性能略為增加。增加的Ra導致高黏附強度但不佳的訊號傳輸性能。由這些結果,據信較高的Ra導致較多數量之從表面向外突出的橫向突出物形成。When Ra is low (Example 39), the adhesion strength decreases but the signal transmission performance slightly increases. Increasing Ra results in high adhesion strength but poor signal transmission performance. From these results, it is believed that higher Ra leads to the formation of a greater number of lateral protrusions protruding outward from the surface.
無表面高台的金屬層(比較例1)與創新的金屬層相比具有不佳的物理性能。The metal layer without surface plateaus (Comparative Example 1) has inferior physical properties compared to the innovative metal layer.
雖然已詳細描述本發明的具體內容,但對於本發明所屬技術領域中具有通常知識者而言明顯的是,這些具體內容僅是較佳實施例,並非旨在限制本發明的範圍。因此,本發明的真正範圍是由附加請求項及其等同物來界定。Although the specific contents of the present invention have been described in detail, it is obvious to those with ordinary knowledge in the technical field to which the present invention belongs that these specific contents are only preferred embodiments and are not intended to limit the scope of the present invention. Therefore, the true scope of the present invention is defined by the appended claims and their equivalents.
100:金屬層 10:突出物 11:凸起 11a:微突出物 12:高台 a:底部長度 b:高度 c:長度 100: metal layer 10: protrusion 11: bulge 11a: micro protrusion 12: platform a: bottom length b: height c: length
圖1示出根據本發明的一個實施例的金屬層的表面的一部分。 圖2示出根據本發明的一個實施例的金屬層的突出物的可能形狀。 圖3示出測試例1中示例1和比較例1的金屬層之掃描電子顯微鏡(SEM)和離子束截面拋光(CP)的結果。 FIG. 1 shows a portion of the surface of a metal layer according to an embodiment of the present invention. FIG. 2 shows a possible shape of a protrusion of a metal layer according to an embodiment of the present invention. FIG. 3 shows the results of scanning electron microscopy (SEM) and ion beam cross-sectional polishing (CP) of the metal layers of Example 1 and Comparative Example 1 in Test Example 1.
無without
100:金屬層 100:Metal layer
10:突出物 10: Protrusions
11:凸起 11: Bump
11a:微突出物 11a: Microprotrusions
12:高台 12: High platform
a:底部長度 a: Bottom length
b:高度 b:Height
c:長度 c: Length
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- 2022-06-09 KR KR1020220070321A patent/KR20230169770A/en unknown
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2023
- 2023-06-09 TW TW112121525A patent/TW202415167A/en unknown
- 2023-06-09 WO PCT/KR2023/007918 patent/WO2023239194A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
KR20230169770A (en) | 2023-12-18 |
WO2023239194A1 (en) | 2023-12-14 |
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