TW201432093A - 有機保焊劑及方法 - Google Patents
有機保焊劑及方法 Download PDFInfo
- Publication number
- TW201432093A TW201432093A TW102147139A TW102147139A TW201432093A TW 201432093 A TW201432093 A TW 201432093A TW 102147139 A TW102147139 A TW 102147139A TW 102147139 A TW102147139 A TW 102147139A TW 201432093 A TW201432093 A TW 201432093A
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- decyl
- salts
- substituted
- osp
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 37
- 239000003755 preservative agent Substances 0.000 title abstract description 4
- 230000002335 preservative effect Effects 0.000 title abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 72
- 229910052802 copper Inorganic materials 0.000 claims description 71
- 239000010949 copper Substances 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 58
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 28
- 125000000623 heterocyclic group Chemical group 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- -1 nitro, hydroxy Chemical group 0.000 claims description 21
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 19
- 125000005843 halogen group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000007970 thio esters Chemical class 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims description 2
- 150000003378 silver Chemical class 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 150000003216 pyrazines Chemical class 0.000 abstract 1
- 238000005476 soldering Methods 0.000 description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 28
- 229910000679 solder Inorganic materials 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- FHHCKYIBYRNHOZ-UHFFFAOYSA-N 2,5-diphenyl-1h-imidazole Chemical compound C=1N=C(C=2C=CC=CC=2)NC=1C1=CC=CC=C1 FHHCKYIBYRNHOZ-UHFFFAOYSA-N 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000009472 formulation Methods 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 150000001556 benzimidazoles Chemical class 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- 239000011241 protective layer Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGMPVYSXXIOGJY-UHFFFAOYSA-N Fusaric acid Chemical compound CCCCC1=CC=C(C(O)=O)N=C1 DGMPVYSXXIOGJY-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000000707 boryl group Chemical group B* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
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- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 235000005985 organic acids Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HEUUBWQOIYCBCI-UHFFFAOYSA-N 2h-benzotriazole;copper Chemical compound [Cu].C1=CC=CC2=NNN=C21 HEUUBWQOIYCBCI-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
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- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
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- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
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- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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Abstract
有機保焊劑溶液包括抑制金屬腐蝕的吡□衍生物。該溶液施用至電子裝置組件的金屬表面，以改良在該電子裝置中之組件間之電氣連接的可焊性。
Description
本發明係有關於有機保焊劑及塗佈銅及銅合金表面之方法。更明確言之，本發明係有關於有機保焊劑及塗佈銅及銅合金表面之方法，其中該有機保焊劑包括吡衍生物。
銅及其合金乃電子應用中最常用金屬，諸如提供印刷電路板(PCB)的傳導電路路徑。印刷電路板要求藉由焊接操作以將電子組件附接至銅及銅合金表面襯墊或貫穿孔。含鉛組件可插入貫穿孔內，接著波焊；或表面黏著技術(SMT)組件可附接至表面襯墊，其方式係經由例如藉由網印而施用焊膏至該表面，然後將該組件置於焊膏上，接著為迴流焊(reflow)。針對SMT組裝件操作，要求至少兩個迴流焊週期以附接組件至PCB的前及後兩側。針對更複雜的組裝件，可能要求額外迴焊操作以附接額外組件，或進行修復操作。
組件安裝於其上的PCB襯墊之銅表面典型地係以保護性金屬或非金屬的光整(或稱精加工)塗佈。此種保護性光整係設計以藉由於PCB製造後的儲存期間，或於暴露於焊接溫度期間，防止銅表面被氧化而維持良好焊接性。
保護性光整可施用至PCB的方法有數種：藉由從溶
液將金屬電解沈積、非電解沈積、或浸沒沈積；或藉由於沈積保護性有機保焊劑的溶液中之浸沒處理(OSP)，或於熔融焊料合金之浴中以稱作為熱空氣(焊接)整平(HAL/HASL)的製程處理。
因經塗佈之襯墊具有優異表面共面性之故，OSP被視為低成本SMT可相容之非金屬的表面光整法。目前PCB產業使用的OSP主要係以唑化合物為基底，諸如咪唑類、苯并咪唑類及其衍生物。
全部此等N-雜環化合物皆係透過與銅原子形成共價鍵而吸附至銅表面上，及有能力透過銅-N-雜環錯合物的生成而形成較厚膜。OSP薄膜形成較佳地為銅專一性，在金或其它表面上具有明顯更低的薄膜形成速率，以防止於銅上形成薄膜之製程期間此等基板的污染。概略言之，OSP塗佈層厚度係為80奈米(nm)至500奈米。更薄的塗佈層容易降低對抗銅表面氧化的保護效果，而更厚的塗佈層容易導致焊接能力的劣化。
OSP製程持續一代代地演進以達到漸增苛刻的效能要求係歸因於已經合成的N-雜環化合物衍生物之多樣性。目前用於OSP製程的唑化合物已經演進至少五代。
以苯并三唑為基底的樂思公司(Enthone)防銅銹蝕產品恩特克(ENTEK)CU-56係在1960年代首次用作為OSP。參考Soldering and Surface Mount Technology，7(2)，6-9，1995。形成於銅上的苯并三唑之厚度通常小於10奈米。此外，苯并三唑-銅錯合物的分解溫度低，亦即約為75℃，而且保護層典型地只耐受單一錫-鉛熱迴流焊週期。
使用經取代之咪唑作為活性成分的第二代係在1977
年問市。參考美國專利第3,933,531號。此等材料形成厚度大於0.2微米的OSP薄膜，但於較高溫具有相對不佳的安定性。
使用苯并咪唑，其中苯環與咪唑環稠合，第三代OSP化合物係在1990-1991年問市。參考美國專利第5,173,130號。苯并咪唑類已經由PCB產業的許多公司廣泛用於許多商業OSP產品作為主要成分。苯并咪唑類非常有效率地與銅形成錯合物，具有膜厚度係在10奈米至100奈米之範圍。藉由將金屬離子加入工作溶液可將厚度進一步增加至500奈米至600奈米。但苯并咪唑類的沈積選擇性仍為不佳，及於選擇性無電鎳浸漬金(ENIG)製程中OSP塗佈層形成於金表面上。
由於面板設計技術的複雜，要求更多個迴流焊週期以附接額外組件及進行再加工操作。據此，需要進一步改良OSP塗佈層的熱安定性。已發展第四代OSP。此等OSP係為經取代之苯并咪唑類，諸如2-經取代之苯并咪唑類，而且於1997年於業界問市。藉由將經取代基導入苯并咪唑環而大大改良OSP的耐熱性。此等有機銅錯合物的分解溫度顯著地升高，亦即約為350℃，結果導致於100至300奈米厚度範圍之銅上之膜安定性極高。
數種不同辦法已為供應商用來減少金表面上的OSP膜的生成。2003年溫吉羅斯(Wengenroth)取得含苯并咪唑衍生物的預浸組成物的用途之專利，其加速隨後於銅表面上的OSP膜的生成。加速的薄膜生成允許於主OSP浴內使用較低濃度的活性材料，因而減少於金表面上的薄膜的生成。業經發現基於主浴生成之修改的方式是有效的，四國(Shikoku)因而商業化基於使用鐵添加物的數種產品。
1990年代日本已經開始出現PCB組裝件產業朝向無鉛焊接的偏移因2003年歐盟有害物質限用指令(European Union RoHS Directive)的要求而更為加速。如此迫使焊接製程朝向無鉛合金偏移，要求比錫鉛合金高約30℃的迴流焊峰溫。受此迴流焊峰溫升高的驅使，發展出使用芳基-苯基咪唑作為活性成分的第五代OSP。此等OSP之熱安定性及沈積選擇性二者都有改良。雖然今日已有廣泛多種以唑化合物為基底的OSP產物，諸如咪唑類、苯并咪唑類及其衍生物，但仍然需要改良OSP組成物及方法的效能。
組成物包括選自於銅鹽、錫鹽、鋅鹽、銀鹽、鎳鹽、鉛鹽、鋇鹽、錳鹽、鐵鹽及鈀鹽中之一種或多種金屬離子來源、一種或多種酸及具有下式之一種或多種化合物：
其中R1、R2及R3係獨立地為氫、鹵基(halide)、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R1及R2可與其全部原子一起形成五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子；及R1可具有以下結構：
其中R4及R5係獨立地為氫、鹵基、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R4及R5可與其全部原子一起形成五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子。
方法包括提供含銅或銅合金的基板；將該基板與組成物接觸以在該基板的銅或銅合金上形成塗佈層，該組成物包括選自於銅鹽、錫鹽、鋅鹽、銀鹽、鎳鹽、鉛鹽、鋇鹽、錳鹽、鐵鹽及鈀鹽中之一種或多種金屬離子來源、一種或多種酸及具有以下結構之一種或多種化合物：
其中R1、R2及R3係獨立地為氫、鹵基、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R2及R3可與其全部原子一起形成五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子；及R1可具有以下結構：
其中R4及R5係獨立地為氫、鹵基、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R4及R5可與其全部原子一起形成五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子。
該等組成物及方法能在銅及銅合金表面上形成連續和實質上均勻的有機薄膜。該薄膜具有良好抗蝕性及熱安定性，且即便於多個加熱週期之後仍然保有銅及銅合金表面的可焊性。另外，該等組成物可用作為預浸物，預浸物係在一種或多種習知OSP組成物之施用前施用至銅或銅合金。該預浸物加強在銅或銅合金上的最終保護性塗佈層。
如用於本說明書全文，除非上下文另行明確指示，否則如下列舉的縮寫具有下列定義：g=公克；mL=毫升；L=公升；cn=厘米；nm=奈米；min.=分鐘；ppm=每百萬份之份數；℃=攝氏度數；RT=室溫；RO=逆滲水；mol=莫耳；g/L=每公升的公克數；OSP=有機保焊劑；ORL0=不含鹵化物的有機助焊劑；ROL0=不含鹵化物的松香助焊劑；FTIR(ATR-FTIR)=衰減式全反射傅立葉轉
換紅外線光譜術(attenuated total reflection Fourier transformed infrared spectroscopy)；FIB=聚焦離子束光譜術；XPS=X射線光電子光譜術；1H-NMR=質子核磁共振；B=硼元素；Si=矽元素；及wt%=百分重量比。
「印刷電路板」及「印刷佈線板」二詞於全文說明書中係互換使用。「鍍覆」及「沈積」二詞於全文說明書中係互換使用。「結構」及「式」二詞於全文說明書中係互換使用。「一(a)」及「一(an)」二詞係指單數及多數二者。除非另行陳述，否則全部用量皆為以重量計。全部數值範圍皆為包含邊值且可以任何順序組合，但邏輯上此等數值範圍係受限於加總為100%。
該等組成物可於電子組件諸如印刷電路板的製造中用作有機保焊劑。該等組成物係施用至基板的銅或銅合金表面以塗佈該等表面，及保護該等表面免於組裝之前的儲存期間以及隨後之組裝操作期間於附接電子組件期間被氧化。該等組成物為以水性為基底，及排除有機溶劑。組成物包括具有以下結構的一種或多種化合物：
其中R1、R2及R3係獨立地為氫、鹵基、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R1及R2可與其全部原子一起形成
五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子；及R1可具有以下結構：
其中R4及R5係獨立地為氫、鹵基、硝基、羥基、氰基、經取代或未經取代之直鏈、分支鏈或環狀烴基、經取代或未經取代之直鏈或分支鏈烷氧基、羧基、酯基、巰基、烷硫基、硫酯基、胺基、醯胺基、硼烷基或矽烷基；R4及R5可與其全部原子一起形成五員雜環系環，其中該雜環系環包括兩個氮原子作為雜原子。
當R2與R3一起形成五員雜環系環時，化合物具有以下結構：
其中R1係如前文定義，及R6係與R1相同，但限制條件為R6非為如上式II之結構。
當結構I之R1為如前文定義的結構II時，化合物之結構係為如下：
其中R2、R3、R4及R5係如前文定義。
當R4與R5一起形成五員雜環系環時，該結構係為如下：
其中R6係如前文定義。
烴基典型地含有1至25個碳原子，較佳1至12個碳原子，更佳1至7個碳原子。烴基可為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、戊基、己基、庚基、苯基或苄基。經取代之烴基上的取代基包括，但非限於，硝基、胺基、鹵基、氰基、羰基、羧基、羥基及烷氧基。鹵基包括氟基、氯基及溴基，典型地鹵基為氯基及氟基，更典型地鹵基為氯基。
經取代或未經取代之直鏈或分支鏈烷氧基及經取代或未經取代之直鏈或分支鏈胺基及醯胺基可含有1至25個碳原子，較佳1至12個碳原子，及更佳1至6個碳原子。經取代之烷氧基及經取代之胺基及醯胺基上的取代基包括，但非限於，硝基、胺基、鹵基、氰基、羰基、羧基、羥基及烷氧基。
經取代或未經取代之直鏈或分支鏈羧基及羰基可含有1至25個碳原子，較佳1至12個碳原子及更佳1至6個碳原子。取代基包括，但非限於，硝基、鹵基及羥基。
經取代或未經取代之直鏈或分支鏈酯基及硫酯基可具有2至25個碳原子，較佳2至12個碳原子，及更佳2至6個碳原子。取代基包括，但非限於，硝基、鹵基、羥基及氰基。
經取代或未經取代之直鏈或分支鏈烷硫基可含有1至25個碳原子，較佳2至12個碳原子及更佳2至6個碳原子。取代基包括，但非限於，硝基、鹵基、羥基及氰基。
硼烷基具有以下結構：
其中R7及R8獨立地為氫、經取代或未經取代之直鏈或分支鏈烷基(其含有1至10個碳原子，較佳1至5個碳原子)，最佳R7及R8為氫。取代基包括，但非限於硝基、羥基及鹵基。
矽烷基具有以下結構：
其中R9、R10及R11獨立地為氫，或經取代或未經取代之分支鏈或直鏈之烷基(其含有1至5個碳)；或苯基。較佳地，R9、R10及R11為具有1至4個碳之烷基或苯基。此等矽烷基之實例為三甲基矽烷基、第三丁基二苯基矽烷基、第三丁基二甲基矽烷基及三異丙
基矽烷基。取代基包括，但非限於，鹵基、硝基及羥基。
較佳地，R1、R2及R3獨立地為氫、羥基、含1至6個碳原子之經取代或未經取代之直鏈或分支鏈烷基或烷氧基。烷基或烷氧基上之取代基包括，但非限於，羥基、羧基、胺基及羰基。最佳地，R1、R2及R3獨立地為氫、羥基、含1至5個碳原子之經取代或未經取代之直鏈或分支鏈烷基，其中該等取代基包括，但非限於，羥基及胺基。最佳地，R1、R2及R3獨立地為氫、羥基或含1至5個碳原子之羥基烷基。又更佳地為R1、R2及R3為氫。
具有前述結構之吡衍生化合物可以0.5公克/公升至15公克/公升，較佳地1公克/公升至12公克/公升，更佳地2公克/公升至10公克/公升之用量含括於組成物。此等化合物可為商業上獲得，或可依據發明所屬技術領域中已知之方法或參考文獻中揭示之方法製備。
組成物也可包括一種或多種酸，較佳為有機酸，以調整組成物之pH至1至6，較佳地1至5，更佳地2至4之範圍。無機酸包括，但非限於，氫氯酸、硫酸、硝酸、磷酸及氫氟酸。有機酸包括，但非限於，羧酸及其鹽類。此等羧酸包括，但非限於，乙酸、檸檬酸、酒石酸、抗壞血酸、蘋果酸、甲酸及其鹽類。一般而言，無機酸及有機酸係以0.1公克/公升至10公克/公升之用量含括於組成物；但因酸係以足量含括來維持期望的pH，故其用量可改變。
一種或多種金屬離子來源也可含括於組成物。含括金屬離子來增加薄膜的形成速率，提供更均勻的薄膜層及也降低
組成物的操作溫度。此等金屬離子包括，但非限於，銅、錫、鋅、銀、鎳、鉛、錳、鋇、鈀及鐵。較佳地，金屬離子係選自於銅、錫、鋅、銀、錳、鐵及鎳。更佳地金屬離子係選自於銅、鋅、錫、及鎳。最佳地，金屬離子係選自銅及鋅。金屬離子來源可含括任何水溶性有機或無機金屬鹽，諸如鹵化物之水溶性金屬鹽、硝酸鹽、乙酸鹽、硫酸鹽、氧化物、烷基磺酸鹽、甲酸鹽、葡萄糖酸鹽、酒石酸鹽、草酸鹽、乙酸鹽、及乳酸鹽。許多此等金屬鹽類為商業上可得或可根據參考文獻之揭示製備。一般而言，此等鹽類係以0.001公克/公升至5公克/公升，較佳地0.01公克/公升至2公克/公升之用量含括於組成物。此等鹽類係以提供1ppm至5000ppm，較佳地10ppm至2000ppm濃度金屬離子之量添加。
視需要地，一種或多種錯合劑或螯合劑可含括於該組成物。可使用習知錯合劑或螯合劑。此等錯合劑或螯合劑包括，但非限於，羧酸類，諸如乙酸、甲酸、氮基-三乙酸、酒石酸、葡萄糖酸、鄰苯二甲酸、檸檬酸、伸乙基二胺四乙酸(EDTA)、及N-(2-羥基乙基)伸乙基二胺-N,N’,N’-三乙酸三鈉鹽(HEDTA)；經羧酸取代之含N雜環系化合物諸如吡啶甲酸、喹啉酸、菸鹼酸、芙莎酸(fusaric acid)、異哌啶酸、吡啶二羧酸、哌羧酸、吡咯羧酸及吡咯啶；胺基羧酸類包括，但非限於，多胺類、胺基醇類，諸如乙醇胺及二甲基乙醇胺；含硫化合物諸如硫醇類、二硫化物、硫醚類、硫醛類、硫酮類、硫脲及其衍生物、硫二醇類、巰基乙酸、巰基丙酸及巰基丁二酸；胺類諸如伸乙基二胺及氨；及胺基酸類諸如麩胺酸、天冬胺酸、離胺酸、組胺酸、丙胺酸、甘胺酸、麩胺酸、纈胺酸、半胱胺酸及蛋胺酸。
於施用該組成物至該基板的銅或銅合金表面之前，該金屬表面典型地經清潔或蝕刻或經清潔且經蝕刻以去除有機污染及表面氧化。合宜的清潔劑包括酸組成物，諸如彼等含括鹽酸、硫酸、檸檬酸者、及鹼性表面處理諸如彼等含括氫氧化鈉、碳酸氫鈉及碳酸鈉者。此種清潔組成物可含有已公開之參考文獻中揭示的濕潤劑或其它成分。此種清潔典型地係於室溫5至10分鐘內完成。然後該基板視需要地使用水清洗，然後使用含氧化劑之溶液微蝕刻以粗化該表面。此等氧化劑為發明所屬技術領域及參考文獻中周知。氧化劑之實施例為過硫酸鈉之硫酸水溶液。蝕刻典型地係於室溫至30℃進行0.5至2分鐘。基板可經清洗及乾燥。
然後OSP組成物藉由發明所屬技術領域中已知之任一種適當方法施用至金屬。此種方法包括，但非限於，將該基板浸沒於組成物內，將該組成物噴灑至基板上，或將組成物刷塗至基板上。一般而言，OSP係於室溫至90℃，較佳30℃至70℃之溫度施用。於下個處理步驟之前，基板與OSP間之接觸時間可於1分鐘至10分鐘，較佳地1分鐘至5分鐘之範圍。視需要性地經塗佈之基板可於室溫風乾然後該基板可於室溫以水清洗，接著於50至70℃溫度藉由熱空氣風乾。金屬表面上已乾燥的薄膜典型地形成80奈米至400奈米厚，更典型地100奈米至300奈米厚的均勻層。最典型地，已乾燥之薄膜具有100奈米至200奈米之厚度。
該組成物及方法可用以在銅及銅合金上形成OSP抗蝕薄膜。銅合金包括，但非限於，銅/錫、銅/鋅、銅/錫/鋅、銅/錫/銀及銅/鎳。較佳地，OSP係施用至銅。雖然OSP典型地用於印刷電路板的製造，但也可用在其它防蝕抑制成問題之含銅及含
銅合金之基板上。
OSP之施用後可接著為焊接法。可使用任一種適當焊接法。焊接可藉由加熱、氣相、雷射、電漿、烤爐熔解、或電流通過焊接金屬或金屬合金而完成，或藉由將焊接金屬及金屬合金加熱至高於其液化溫度之任一種其它方法完成。典型地使用錫-鉛或不含鉛之焊接法。
於另外具體例中，於將習知OSP施用至銅或銅合金之前，含有吡衍生物之組成物可用作為預浸組成物或前處理組成物。預浸物係在使用氧化劑蝕刻後施用至銅或銅合金以塗佈該金屬。基板於蝕刻後可視需要地經清洗。預浸物施用至金屬歷10秒至5分鐘，較佳地15秒至2分鐘。預浸物係於室溫至90℃，較佳室溫至60℃之溫度施用。視需要地，清洗基板，然後如前文描述施用習知OSP至該金屬。習知OSP調配物可包括三唑類、咪唑類、及苯并咪唑類。此等調配物之實施例係揭示於美國專利第5,362,334號；美國專利第5,376,189號及美國專利第5,658,611號。然後該等基板如前文描述進行焊接。
該等組成物及方法允許於金屬表面上形成連續且實質上均勻的有機薄膜。該薄膜具有良好抗蝕性及熱安定性，而且即便經過多個加熱週期之後仍然保有銅及銅合金表面的可焊性。
下列實施例並非意圖限制本發明之範疇，反而係進一步闡明本發明。
1H-咪唑[4,5-b]吡化合物之製法係經由混合2公克2,3-二胺基吡及10毫升原甲酸三乙酯，然後於氮下於140至145℃迴流
焊2小時。反應混合物經冷卻，過濾及以己烷洗滌。所得固體於100℃溶解於10毫升10%氫氧化鈉溶液10分鐘，及趁熱過濾。添加10毫升乙酸至濾液，然後於室溫儲存隔夜。藉由過濾而收集淺褐色晶體，產率為75%或1.64公克。參考J.Am.Chem.Soc.,78,242-244,1956。該產物使用1H-NMR(布魯克(Brucker)阿德凡斯(ADVANCE)III 400MHz)及質譜術(社摩(Thermo)菲尼根(Finnigan)MAT 95XL)證實為從乙酸再結晶的1-H-咪唑[4,5-b]吡。
OSP溶液係如後文說明製備。
含5公克/公升1-H-咪唑[4,5-b]吡及100ppm銅離子之工作浴製備如下：1.依據實施例1所述方法製備的1公克1-H-咪唑[4,5-b]吡使用100毫升逆滲透水溶解於250毫升燒杯中；2.溶液攪拌至固體溶解為止(混合物A)；3.混合物A之pH使用50%乙酸調整至2.5；4.於容積瓶中製備10公克/公升氯化銅(II)二水合物溶液，然後2毫升此氯化銅溶液轉移入混合物A中；及5.添加足量逆滲透水至混合物A以將體積調整至200毫升。
得自菲斯平特(Fastprint)中國公司的三個FR-4銅包
積層物使用OSP浴，及根據下表2揭示之方法處理。
該等積層物中之二者受到迴流焊處理。一個積層物迴流焊5次，及另一個積層物迴流焊11次。麻康(MALCOM)桌上型迴流焊烤爐使用255℃的峰溫。斜坡升溫速率為40℃至200℃=1℃/秒及200℃至250℃=1.3℃/秒。迴流焊參數及程序係如表3所述。
然後FIB用以測量塗佈層厚度及從積層物之剖面研
究各個積層物塗佈層的連續性。經測定在全部三個積層物上的OSP層皆為連續且均勻的，而且於各個積層物上具有120奈米之厚度。進行5個迴流焊週期的積層物於迴流焊之後，仍然具有連續且均勻的OSP厚度為120奈米。於受到11個加熱週期的積層物上發現均勻且連續的OSP厚度為110奈米。
重複實施例2所述方法，但所使用的OSP為0.04莫耳/公升之2,4-二苯基-1H-咪唑調配物。測試三個OSP試樣。
一個試樣未進行迴流焊，及具有600奈米連續且均勻的OSP厚度。第二試樣也具有600奈米的連續且均勻的OSP厚度，及第三試樣具有200奈米的連續且均勻層。5個迴流焊週期後，第二OSP試樣的厚度為500奈米，因此與未經迴流焊的積層物之OSP厚度相比並無顯著改變；但觀察到OSP塗佈層的分層(delamination)。11個迴流焊週期後，第三個經處理的積層物具有170奈米的OSP厚度，其為連續但不均勻的。此外，觀察到OSP塗佈層的分層。
提供8個FR-4銅包積層物。各個積層物使用羅那克林LP-200酸清潔劑清潔。其中四個積層物使用實施例2之OSP調配物及製程處理。其餘四個積層物未經處理及用作為對照組。接受OSP浴處理的積層物中之三者通過迴流焊處理。一者迴流焊3次，另一者迴流焊5次，及第三者迴流焊11次。迴流焊條件係與實施例2描述者相同。以OSP處理的一個積層物並未進行任何迴流焊加工。未經處理的積層物中之三者也在如同該等三個經OSP處理的
積層物之相同條件下迴流焊。一者迴流焊3次，另一者迴流焊5次，及第三者迴流焊11次。
相較於對照組未經迴流焊處理的積層物，進行迴流焊的三個對照組積層物全部皆顯示嚴重銅變色。該變色表示氧化。進行3次迴流焊的積層物具有大塊銅變色斑塊。進行5次迴流焊的積層物的表面超過一半變色，及在迴流焊11次的積層物中觀察到最嚴重變色。實質上，整個表面皆變色。相反地，經OSP處理的全部積層物皆具有可觀察到完全覆蓋銅表面的OSP塗佈層，而且即便於11個迴流焊週期之後，仍然實質上無變色。因此，即便於苛刻的迴流焊條件下，OSP塗佈層可抑制銅的氧化及顯示良好熱安定性。
重複實施例4描述的製程，但所使用的OSP為2,4-二苯基-1H-咪唑調配物。處理八個FR-4銅包積層物。經處理之積層物中之6者迴流焊3次、5次或11次，每個迴流焊周期有兩塊積層物。未進行迴流焊處理的兩塊積層物並未出現變色，及OSP覆蓋積層物的全體表面。於經進行3次迴流焊的調配物處理的一個積層物中觀察到小量變色；但進行三個迴流焊週期的第二積層物並未顯示任何目測可見的氧化徵象。進行5次迴流焊的積層物顯示小量銅氧化；但進行11個迴流焊週期的兩個積層物顯示顯著銅氧化。因此，相較於2,4-二苯基-1H-咪唑OSP調配物，1H-咪唑[4,5-b]吡OSP具有較佳熱安定性。
提供12塊FR-4銅包積層物。其中三塊板使用如同實施例2
之OSP浴及方法處理。六塊積層物根據實施例2之表2所述製程，以0.04莫耳/公升2,4-二苯基-1H-咪唑處理。三塊積層物未經處理，但其中兩塊受到5次及11次迴流焊。以兩種OSP中的一種處理的6塊積層物進行5個或11個迴流焊週期。以1H-咪唑[4,5-b]吡處理的一塊積層物並未進行迴流焊，及以2,4-二苯基-1H-咪唑處理的兩塊積層物並未進行迴流焊。然後以ATR-FTIR分析全部積層物的熱安定性，以測量與銅氧化相關連的於640cm-1之峰大小。於640cm-1的峰強度愈高，則銅氧化愈大。未以兩種OSP中之一種處理的全部三塊積層物皆顯示於640cm-1的特性銅氧化峰，未經處理的積層物之峰強度係大於以兩種OSP調配物中之一種處理的積層物之峰強度。以2,4-二苯基-1H-咪唑處理的全部積層物之此峰強度皆係大於進行迴流焊的四塊積層物之峰強度。針對受到11個迴流焊週期之兩塊積層物，則觀察到最大強度。
由於吡的擺動，以含1H-咪唑[4,5-b]吡的OSP浴處理的積層物顯示於635cm-1之峰，並且表示一些銅氧化。針對進行11次迴流焊的積層物，峰強度略微增高。此等三個積層物的氧化係不如未經處理的積層物及以2,4-二苯基-1H-咪唑處理的積層物的氧化嚴重。因此，相較於未經處理的積層物及以2,4-二苯基-1H-咪唑調配物處理的積層物，含括1H-咪唑[4,5-b]吡之OSP浴顯示改良之熱安定性。
X射線光電子光譜術(XPS)用以評估塗佈層中的元素分布及由於熱迴流焊所造成的變化。針對不含任何保護層的裸露銅層積層物，XPS結果顯示氧可容易地與該表面反應而於5個迴流焊週
期之後形成銅氧化層。有效保護層可防止銅的氧化。
提供11塊FR-4積層物來測試含1-H-咪唑[4,5-b]吡之OSP浴及其相對於未經處理的及含2,4-二苯基-1H-咪唑的OSP調配物的抑制氧穿透入銅的能力。兩塊積層物未經OSP調配物處理。一塊於開放空氣環境中蝕刻。第二塊使用實施例2中表3揭示的製程於蝕刻後以5個迴流焊週期迴流焊。未經迴流焊的積層物表面之氧含量測得為30原子%，表示顯著銅氧化。銅層內部的氧含量測定為1至5原子%，表示若干銅氧化。進行迴流焊的積層物於其表面上具有30原子%的氧含量，而內銅層具有25原子%的氧含量，表示於迴流焊後氧含量顯著增高及銅層內部的銅氧化增加。
三塊積層物以實施例2中表1的OSP浴處理及以上表2揭示的方法加工。迴流焊經處理的積層物中的兩塊。其中一塊迴流焊5次，及另一塊迴流焊11個週期。蝕刻未經迴流焊的積層物及兩塊經迴流焊的積層物，及使用XPS測定各個積層物中之原子%氧含量。銅表面的原子氧含量測定為25原子%，表示於表面上形成氧化銅。但銅層內部測得的氧含量測定為0原子%，如此並無任何銅層內部形成氧化銅之指標。比較對照組積層物，含有1-H-咪唑[4,5-b]吡的OSP浴可防止氧穿透入銅表面，如此能夠抑制銅的氧化。
其餘6塊積層物以0.04莫耳/公升2,4-二苯基-1H-咪唑處理。四塊以5個或11個週期迴流焊，及兩塊未經迴流焊。如XPS方法所測量，未經迴流焊的積層物及迴流焊5個週期的積層物並無顯示任何氧穿透作用之指標。但針對迴流焊11個週期的兩
塊積層物，銅層內部的氧含量從5原子%升高至8原子%，表示氧化銅的形成。因此，相較於以2,4-二苯基-1H-咪唑處理且迴流焊11次的積層物，以1-H-咪唑[4,5-b]吡OSP處理及迴流焊11次的積層物具有改良的效能。
提供18塊FR-4銅包積層物以測試兩種OSP調配物的可焊性效能。使用的助焊劑為凱斯特(KESTER)979(ORL0)或KESTER 985M(ROL0)。用在各個積層物上的焊料為賽克(SAC)305焊料，其組成為96%錫、3.5%銀及0.5%銅，得自日本(Nihon)蘇沛銳(Superior)SN97C。一種調配物具有實施例2中表1揭示的組成及另一種調配物包含0.04莫耳/公升，2,4-二苯基-1H-咪唑。六塊積層物經1-H-咪唑[4,5-b]吡OSP處理，及12塊積層物經2,4-二苯基-1H-咪唑處理。處理程序係與如上實施例2中表2揭示的程序相同。積層物以兩種調配物中之一者處理，及以兩種助焊劑中之一種助焊。六塊積層物插入255℃焊接盆(solder pot)內來將積層物塗佈焊料。全部積層物皆以焊料100%塗覆；但以2,4-二苯基-1H-咪唑OSP處理的積層物之濕潤效能顯示為較佳。此點係由以2,4-二苯基-1H-咪唑處理的積層物出現光滑焊料塗佈層決定。相反地，以1-H-咪唑[4,5-b]吡塗佈的兩塊積層物具有粗糙外觀之焊接表面。
於施用焊料之前，於施用兩種OSP中之一者之後，其餘積層物經過迴流焊。六塊迴流焊5次及另外六塊迴流焊11次。於迴流焊之後，積層物使用兩種助焊劑中之一種助焊，接著使用焊料塗覆。使用含有1-H-咪唑[4,5-b]吡的OSP處理的四塊積層物顯示良好濕潤效能。兩塊迴流焊5次的積層物具有100%焊
料覆蓋率。迴流焊11次的一塊積層物也具有100%焊料覆蓋率，而使用凱斯特985M助焊的另一塊積層物具有95%覆蓋率。此外，焊料覆蓋呈現光滑。
相反地，以2,4-二苯基-1H-咪唑OSP處理及迴流焊5次的一塊積層物顯示針對凱斯特979焊料之90%焊料覆蓋率及一塊積層物顯示針對凱斯特985M焊料之70%覆蓋率。以凱斯特979助焊劑處理的另一塊積層物具有100%覆蓋率；但以凱斯特985M處理的一塊積層物只有80%覆蓋率。迴流焊11次且以凱斯特979處理的一塊積層物具有80%覆蓋率，及以凱斯特985M處理的一塊積層物只有15%覆蓋率。迴流焊11次及以凱斯特979助焊劑處理的一塊積層物具有70%覆蓋率，以凱斯特985M助焊劑處理的另一塊積層物只有10%覆蓋率。以2,4-二苯基-1H-咪唑OSP處理的積層物之焊料覆蓋率減低，表示OSP塗佈層的劣化及OSP層的氧含量增高而有損焊料覆蓋率。因此，相較於習知2,4-二苯基-1H-咪唑OSP，包含1-H-咪唑[4,5-b]吡之OSP浴於迴流之後顯示改良的焊料覆蓋率，如此表示該等1-H-咪唑[4,5-b]吡OSP層中的氧含量減低。
Claims (5)
- 一種組成物，包含選自於銅鹽、錫鹽、鋅鹽、銀鹽、鎳鹽、鉛鹽、鋇鹽、錳鹽、鐵鹽及鈀鹽中之一種或多種金屬離子來源、一種或多種酸及具有下式之一種或多種化合物：
- 如申請專利範圍第1項所述之組成物，其中，該一種或多種化合物係以0.5公克/公升至15公克/公升之用量含括於該組成物中。
- 如申請專利範圍第1項所述之組成物，其中，該一種或多種金屬離子來源係以0.001公克/公升至5公克/公升之用量含括於該組成物中。
- 一種方法，其係包含：a)提供包含銅或銅合金的基板；及b)將該基板與組成物接觸以在該基板的該銅或銅合金上形成塗佈層，該組成物包括選自於銅鹽、錫鹽、鋅鹽、銀鹽、鎳鹽、鉛鹽、鋇鹽、錳鹽、鐵鹽及鈀鹽中之一種或多種金屬離子來源、一種或多種酸及具有以下結構之一種或多種化合物：
- 如申請專利範圍第4項所述之方法，其中該基板係為印刷電路板。
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| EP (1) | EP2746427B1 (zh) |
| JP (1) | JP6334910B2 (zh) |
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| CN107971655B (zh) * | 2018-01-23 | 2019-12-27 | 永星化工(上海)有限公司 | 一种高抗热性有机保焊剂及其应用 |
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| TWI625425B (zh) * | 2013-12-06 | 2018-06-01 | Mec股份有限公司 | 蝕刻液、補給液以及銅配線的形成方法 |
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| EP2746427B1 (en) | 2015-04-22 |
| CN103882417B (zh) | 2016-01-06 |
| EP2746427A1 (en) | 2014-06-25 |
| KR20140080449A (ko) | 2014-06-30 |
| JP6334910B2 (ja) | 2018-05-30 |
| JP2014140893A (ja) | 2014-08-07 |
| CN103882417A (zh) | 2014-06-25 |
| TWI484069B (zh) | 2015-05-11 |
| US20140174322A1 (en) | 2014-06-26 |
| US8961678B2 (en) | 2015-02-24 |
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