TW201235131A - Solder paste for precoating - Google Patents
Solder paste for precoating Download PDFInfo
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- TW201235131A TW201235131A TW101106027A TW101106027A TW201235131A TW 201235131 A TW201235131 A TW 201235131A TW 101106027 A TW101106027 A TW 101106027A TW 101106027 A TW101106027 A TW 101106027A TW 201235131 A TW201235131 A TW 201235131A
- Authority
- TW
- Taiwan
- Prior art keywords
- solder
- powder
- metal
- good
- precoating
- Prior art date
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 206
- 239000000843 powder Substances 0.000 claims abstract description 178
- 229910052751 metal Inorganic materials 0.000 claims abstract description 96
- 239000002184 metal Substances 0.000 claims abstract description 94
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010931 gold Substances 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052737 gold Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 230000004907 flux Effects 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 24
- 239000004332 silver Substances 0.000 claims description 23
- 239000011247 coating layer Substances 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 12
- 239000010941 cobalt Substances 0.000 abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 8
- -1 sliver Substances 0.000 abstract description 4
- 229910052732 germanium Inorganic materials 0.000 abstract description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 abstract description 2
- 210000004940 nucleus Anatomy 0.000 abstract 3
- 238000005253 cladding Methods 0.000 abstract 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 42
- 229910001432 tin ion Inorganic materials 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 15
- 238000007639 printing Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 229910052684 Cerium Inorganic materials 0.000 description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 238000005476 soldering Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009689 gas atomisation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 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
- 239000010953 base metal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FRKBDVGTLHBNSN-UHFFFAOYSA-N 1,3,2,4lambda2-dioxazastannetidin-2-ium 2-oxide nitrate Chemical compound [Sn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FRKBDVGTLHBNSN-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- ICARQSBNIMOEKE-UHFFFAOYSA-N 3-hydrazinylpropanoic acid Chemical compound NNCCC(O)=O ICARQSBNIMOEKE-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
- 229910020922 Sn-Pb Inorganic materials 0.000 description 1
- 229910008433 SnCU Inorganic materials 0.000 description 1
- 229910008783 Sn—Pb Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- GPFURRDVVQXPAA-UHFFFAOYSA-I [Au](Cl)(Cl)Cl.[Cl-].[Cl-] Chemical compound [Au](Cl)(Cl)Cl.[Cl-].[Cl-] GPFURRDVVQXPAA-UHFFFAOYSA-I 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WQGCFAUZCZTVDM-UHFFFAOYSA-H ruthenium(3+);trisulfate Chemical compound [Ru+3].[Ru+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WQGCFAUZCZTVDM-UHFFFAOYSA-H 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
- B23K35/0266—Rods, electrodes, wires flux-cored
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
- B23K35/0272—Rods, electrodes, wires with more than one layer of coating or sheathing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/368—Selection of non-metallic compositions of core materials either alone or conjoint with selection of soldering or welding materials
Abstract
Description
201235131 六、發明說明 【發明所屬之技術領域】 本發明，係有關於在使用焊錫等之材料來將晶圓對於 被搭載有電子零件等之印刷基板而進行覆晶安裝時，適合 於在形成接合用之焊錫等的材料前而對於印刷基板或晶圓 之電極墊片進行預塗覆之預塗覆用焊錫糊。 【先前技術】 近年來，在電子機器中，係以小型、輕量化爲目的， 而進行有高密度安裝之開發。其中，覆晶安裝（以下，稱 作FC安裝），由於係能夠在電路基板上配置複數之矽晶 片，因此，係成爲能夠進行理想性之高密度安裝。在此 FC安裝中，係透過被稱作突塊之突起物，來將晶圓和被 稱作中介物之印刷基板作接合，乃至於進而將中介物和母 基板作接合。在前者中所使用之突塊，一般係被稱作內突 塊，後者則係被稱作外突塊。 在此FC安裝中，係藉由在被形成於銅（Cu)基底膜等 之突塊安裝部（墊片部）上進行焊錫球或焊錫糊之印刷， 來形成作爲突起電極之突塊，但是，爲了防止焊錫附加部 表面之氧化，以及提升焊錫球之浸濕性，係進行有：在銅 (Cu)之上進行錫（Sn)或銀（Ag)之浸漬電鍍，或者 是進行無電解鎳（Ni) /鈀（Pd) /金（Au)電鍍或無 電解鎳（Ni) /金（Au)電鍍，亦或是預先在焊錫附加 部表面上藉由印刷等來塗布預塗覆用焊錫糊，並經由回焊 -5- 201235131 來將焊錫作預塗覆。 但是，於此所定義之預塗覆用焊錫糊，係爲在內突塊 以及外突塊之墊片部的表面上預先作塗覆之焊錫材料，且 係爲糊狀。 作爲此預塗覆用焊錫糊，於先前技術中，例如在專利 文獻1中，係記載有一種焊錫組成物，其所含有之焊錫粉 末，係被設爲錫以及鉛之共晶形態，且此焊錫粉末之中心 直徑，係被設爲3μιη以上4μιη以下。又，在專利文獻2 中，係記載有一種預塗覆用焊料糊，其係爲將6 3 Sn-Pb或 者是63Sn-2Ag-Pb之焊錫粉末與糊狀助焊劑作了混鍊。 另一方面，由於伴隨著電子零件之細微化，接合零件 之微節距化亦日益進行，因此，例如在專利文獻3中，係 提案有一種焊錫粉末，其係在體積累積頻度達到5 0%的粒 徑（D5〇 )爲5μιη以下之範圍內的錫粉末中，將由銀、 銅、鎳或鍺等之與錫相異種類之金屬所構成並且粒徑 (D5〇)爲較錫粉末之粒徑（d5Q)更小之〇.5μηι以下之範 圍內的金屬粉末’作了至少一種以上之添加混合，所得到 者。此焊錫粉末’係能夠與近年之微節距化相對應，並 且，對於微節距用基板之印刷性亦爲優良。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2008-221304號公報（申 請項1、第0018段落） [專利文獻2]日本特開平8-281472號公報（申請201235131 6. Technical Field of the Invention The present invention relates to a method of forming a joint when a wafer is mounted on a printed circuit board on which an electronic component or the like is mounted by using a material such as solder. A pre-coating solder paste pre-coated with a printed circuit board or an electrode pad of a wafer before use of a material such as solder. [Prior Art] In recent years, in electronic devices, development of high-density mounting has been carried out for the purpose of miniaturization and weight reduction. Among them, flip chip mounting (hereinafter referred to as FC mounting) is capable of performing a high-density mounting ideally because a plurality of germanium wafers can be placed on a circuit board. In this FC mounting, a wafer and a printed substrate called an interposer are joined by a projection called a bump, and the interposer and the mother substrate are further joined. The bumps used in the former are generally referred to as inner protrusions, and the latter are referred to as outer protrusions. In this FC mounting, a bump as a bump electrode is formed by printing a solder ball or a solder paste on a bump mounting portion (pad portion) formed on a copper (Cu) base film or the like, but In order to prevent oxidation of the surface of the solder additional portion and to improve the wettability of the solder ball, immersion plating of tin (Sn) or silver (Ag) on copper (Cu) or electroless nickel is performed. (Ni) / palladium (Pd) / gold (Au) plating or electroless nickel (Ni) / gold (Au) plating, or pre-coating solder paste by printing or the like on the surface of the solder additional portion The solder is pre-coated by reflow soldering -5 - 201235131. However, the solder paste for precoating as defined herein is a solder material which is previously coated on the surface of the pad portion of the inner projection and the outer projection, and is formed into a paste. As a solder paste for precoating, in the prior art, for example, Patent Document 1 describes a solder composition in which a solder powder is a eutectic form of tin and lead. The center diameter of the solder powder is set to 3 μm or more and 4 μm or less. Further, Patent Document 2 describes a solder paste for precoating in which a solder powder of 6 3 Sn-Pb or 63Sn-2Ag-Pb is mixed with a paste flux. On the other hand, with the miniaturization of electronic components, the micro-pitch of the bonded components is also increasing. Therefore, for example, in Patent Document 3, a solder powder is proposed which has a volume cumulative frequency of 50%. The tin powder having a particle diameter (D5 〇) of 5 μm or less is composed of a metal different from tin such as silver, copper, nickel or ruthenium, and the particle diameter (D5 〇) is a grain of tin powder. The metal powder in the range of 5 μηι or less is smaller than the diameter (d5Q), and at least one of the above is added and mixed. This solder powder can correspond to micro-pitching in recent years, and is excellent in printability for a micro-pitch substrate. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-221304 (Application No. JP-A No. 8-281472)
S -6 - 201235131 項1、第0025、0027段落） [專利文獻3]日本特開2009-1 90072號公報（申 請項1、2、第0009、〇〇1〇段落） [專利文獻4]日本特開20 04-18956號公報（申請 項1、第0002段落） [專利文獻5]日本特開平6-2641 16號公報（申請 項1、第00016段落、圖3 ) [專利文獻6]日本專利第37445 1 9號公報 [非專利文獻] [非專利文獻1 ]皆川和己、垣澤英樹、木村隆、 馬苣生、唐捷、原田幸明，「無鉛細微球狀粉末的新製造 方法」，第12次「電子產品中.之微接合、安裝技術」， 社團法人熔接學會，平成18年2月，p.113〜ρ·118 【發明內容】 [發明所欲解決之課題] 在上述先前技術中，係殘留有下述之課題。 亦即是，在專利文獻1以及2所記載之預塗覆用焊錫 糊中’係使用含有鉛（Pb)之焊錫粉末，在環境保護的觀 點上係並不理想。現今，在電子零件之接合中所使用的焊 錫，無鉛化係日益進行，關於成爲突塊之焊錫球，亦多所 採用有以錫作爲主成分之焊錫粉末，針對預塗覆用焊錫 糊’亦期望能夠將其無鉛化。又，在專利文獻3中，雖係 提案有能夠以無鉛來充分地對應近年之微節距化的焊錫粉 201235131 末’但是，由於係直接添加有銀等之單一金屬，因此，在 回焊時之熔融性以及浸濕性上，係期望能夠有更進一步的 改良。特別是，係期望能夠發明一種可得到在與銅之基底 膜間的浸濕性或平滑性上爲優良的焊錫膜之焊錫糊。 本發明，係爲有鑑於上述課題所進行者，其目的，係 在於提供一種能夠與微節距化相對應，且爲無鉛化，並且 回焊時之浸濕性、平滑性或者是對於基底金屬之表面被覆 性爲優良的預塗覆用焊錫糊。 [用以解決課題之手段] 本發明，爲了解決上述課題，係採用了下述之構成。 亦即是，本發明之一種預塗覆用焊錫糊，係爲將焊錫粉末 和助焊劑作了混合之預塗覆用焊錫糊，其特徵爲：前述焊 錫粉末，係含有1種、或者是2種以上之金屬粉末，前述 金屬粉末，係分別具備有金屬種互爲相異之中心核、和被 覆前述中心核之被覆層，且平均粒徑爲0.1 μιη以上5μπι 以下，前述中心核，係由銀、銅、鋅、鉍、鍺、鎳、銦、 鈷或者是金之單一金屬所成，前述被覆層，係由錫所成。 在此預塗覆用焊錫糊中，中心核，係由銀、銅、鋅、 鉍、鍺、鎳、銦、鈷或者是金之單一金屬所成，被膜層， 係由錫所成，並含有中心核之金屬種爲相異之1種或2種 以上之金屬粉末，所含有之金屬粉末，係均爲將中心核藉 由錫來作了被覆，相較於將由單一金屬所成之金屬粉末直 接作爲要素粉來作了添加的先前技術之焊錫粉末，在回焊S -6 - 201235131, paragraph 1, 0025, 0027] [Patent Document 3] Japanese Laid-Open Patent Publication No. 2009-190072 (Application No. 1, 2, No. 0009, paragraph 1) [Patent Document 4] Japan Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent No. 37445 1 [Non-Patent Document] [Non-Patent Document 1] Minagawa Kazuyoshi, Sasaki Hideki, Kimura Taka, Makoto, Tang Jie, Harada Yuki, "New Manufacturing Method for Lead-Free Fine Spherical Powder", Twelve times, "Micro-joining and mounting technology in electronic products", Society of Corporate Welding and Welding, February, 1999, p.113~ρ·118 [Summary of the Invention] [Problems to be Solved by the Invention] In the above prior art The following problems remain. In other words, in the solder paste for precoating described in Patent Documents 1 and 2, the use of solder powder containing lead (Pb) is not preferable from the viewpoint of environmental protection. Nowadays, the solder used in the joining of electronic components is becoming more and more lead-free. As for the solder balls to be bumps, solder powder containing tin as a main component is often used, and solder paste for pre-coating is also used. It is expected to be lead-free. In addition, in the case of the patent document 3, it is proposed that the solder powder 201235131 which can sufficiently correspond to the micro-pitch in recent years is provided without lead. However, since a single metal such as silver is directly added, at the time of reflow Further, it is expected that further improvement can be made in terms of meltability and wettability. In particular, it is desirable to invent a solder paste which can provide a solder film excellent in wettability or smoothness with a copper base film. The present invention has been made in view of the above problems, and an object thereof is to provide a lead-free, non-lead, and wettability, smoothness, or base metal for reflow. The surface coating property is an excellent solder paste for precoating. [Means for Solving the Problems] In order to solve the above problems, the present invention adopts the following configuration. In other words, a solder paste for precoating according to the present invention is a solder paste for precoating in which a solder powder and a flux are mixed, and the solder powder is one type or two. In the metal powder, the metal powder includes a center core having a different metal species and a coating layer covering the center core, and an average particle diameter of 0.1 μm or more and 5 μm or less, wherein the center core is Silver, copper, zinc, bismuth, antimony, nickel, indium, cobalt or a single metal of gold, the coating layer is made of tin. In the solder paste for precoating, the central core is made of a single metal of silver, copper, zinc, lanthanum, cerium, nickel, indium, cobalt or gold, and the coating layer is made of tin and contains The metal species of the central core are different one or more metal powders, and the metal powders contained therein are coated with tin from the central core, compared to the metal powder to be formed from a single metal. Prior art solder powder added directly as an elemental powder, in reflow
S -8 - 201235131 時，前述中心核和錫之間的接觸面積係變大。因此，相較 於先前技術之焊錫粉末，其之熔融性以及對於基底膜之浸 濕性係成爲良好，並且，係能夠對於局部性之組成偏差作 抑制。故而，若是使用本發明之預塗覆用焊錫糊，則藉由 相對於基底膜之良好的浸濕性，回焊後之預塗覆用焊錫係 爲薄且爲均一，在平滑性以及對於基底金屬之表面被覆性 上，係爲優良，對於由焊錫球之搭載等所進行的突塊形成 而言，係爲合適。 另外，在將熔點爲較錫更高之單一金屬作爲中心核的 情況時，除了上述的效果之外，藉由將熔點爲高之中心核 以熔點爲低之錫來作被覆，係能夠對於金屬粉末之熔融性 的提升有所助益。 又，在內突塊用之預塗覆中，由於係有必要形成爲小 面積且爲薄，因此，若是先前技術之預塗覆用焊錫糊，則 係難以作對應。故而，內突塊用之預塗覆，在先前技術 中，係使用電鍍法或濺鍍法來形成，然而，係期望能夠實 現一種使用有焊錫糊之簡易的預塗覆。針對此，本發明之 預塗覆用焊錫糊，由於係具備有上述一般之優良特性，因 此’就算是針對先前技術之焊錫糊所無法對應之內突塊， 亦能夠施加良好的預塗覆。 在電子零件接合中所使用之焊錫，係由於環境面的考 量’而進行有無鉛化，現在，係採用將錫作爲主成分之焊 錫粉末。作爲得到如同焊錫粉末一般之細微之金屬粉末的 方法’係週知有：像是氣體霧化法或旋轉圓盤法一般之霧 201235131 化法、或者像是熔紡法、旋轉電極法一般之由機械性製程 所致之方法。氣體霧化法，係在藉由感應爐或氣體爐等而 將金屬熔融後，使熔融金屬從能夠儲存將金屬作了熔融之 熔湯的被稱作餵槽（tundish)之容器底部的噴嘴而流下， 並從其之周圍而吹拂高壓氣體以使其粉化之方法。亦被稱 作旋轉圓盤法之離心力霧化法，係爲使熔融後的金屬落下 至以高速而進行旋轉之圓盤上，並在接線方向上施加剪力 來使其破斷而製作細微粉之方法。 另一方面，伴隨著電子零件之細微化，接合零件之微 節距化亦日益進行，而要求有更加細微之粒徑的焊錫粉 末，因此，關於以此種微節距化作爲目標的技術之改良， 亦係蓬勃發展。例如，作爲將氣體霧化法作了改良之技 術’係揭示有：以將捲入有氣體之狀態下的金屬熔湯從噴 嘴而噴出’並從此噴嘴之周圍而吹拂高壓氣體一事作爲特 徵之金屬微粉末之製造方法（例如，專利文獻4)。若依 據在此文獻中所揭示之方法，則經由在熔湯通過噴嘴時而 將氣體捲入，在熔湯從噴嘴而噴出時，熔湯係已被作了分 斷，而能夠製造出更小的粉末。 又’作爲對於旋轉圓盤法作了改良之技術，係揭示 有：在旋轉體上配置作爲金屬微粉末尺寸調整手段之網 格’並通過此網格來使熔融金屬飛散之金屬微粉末製造方 法（例如’專利文獻5)。若依據在此文獻中所揭示之方 法，則相較於先前技術之旋轉圓盤法，係能夠以良好效率 而產生細微之金屬微粉末。進而，亦提案有將氣體霧化法At S -8 - 201235131, the contact area between the aforementioned center core and tin becomes large. Therefore, compared with the solder powder of the prior art, the meltability and the wettability to the base film are good, and the compositional deviation of the locality can be suppressed. Therefore, in the case of using the solder paste for precoating of the present invention, the solder for precoating after reflow is thin and uniform, in terms of smoothness and for the substrate, by good wettability with respect to the underlying film. The surface of the metal is excellent in coating properties, and is suitable for bump formation by solder ball mounting or the like. Further, in the case where a single metal having a higher melting point than tin is used as the central core, in addition to the above effects, by coating the central core having a high melting point with a tin having a low melting point, it is possible to The increase in the meltability of the powder is helpful. Further, in the precoating for the inner bump, since it is necessary to form a small area and is thin, it is difficult to cope with the solder paste for precoating of the prior art. Therefore, the pre-coating of the inner projections is formed by electroplating or sputtering in the prior art, however, it is desirable to realize a simple pre-coating using a solder paste. In view of the above, since the solder paste for precoating of the present invention has the above-described general excellent characteristics, it is possible to apply good precoating even in the case of the inner bump which the solder paste of the prior art cannot correspond to. Solder used for joining electronic parts is lead-free due to environmental considerations. Now, solder powder containing tin as a main component is used. As a method of obtaining a fine metal powder as a solder powder, it is known that a gas mist atomization method or a rotating disk method generally has a fog 201235131 method, or a melt spinning method or a rotary electrode method. The method of sexual process. The gas atomization method is a method in which a metal is melted by an induction furnace, a gas furnace, or the like, and the molten metal is supplied from a nozzle called a tundish container at the bottom of a container capable of storing molten metal. A method of flowing down and blowing high pressure gas from around it to pulverize it. Also known as the centrifugal force atomization method of the rotating disk method, the molten metal is dropped onto a disk that rotates at a high speed, and a shear force is applied in the wiring direction to break it to prepare a fine powder. The method. On the other hand, with the miniaturization of electronic components, the micro-pitch of the bonded parts is also increasing, and solder powder having a finer particle size is required. Therefore, the technology aimed at such micro-pitching is required. Improvement is also booming. For example, as a technique for improving the gas atomization method, a metal characterized in that a molten metal melted in a state in which a gas is entrained is ejected from a nozzle and a high-pressure gas is blown from the periphery of the nozzle is disclosed. A method of producing a fine powder (for example, Patent Document 4). According to the method disclosed in this document, the gas is entangled by passing the melt through the nozzle, and the melt system is broken when the melt is ejected from the nozzle, and can be made smaller. Powder. Further, as a technique for improving the rotating disk method, there is disclosed a method of manufacturing a metal micropowder in which a mesh of a metal fine powder size adjusting means is disposed on a rotating body and the molten metal is scattered by the mesh. (for example, 'Patent Document 5'). According to the method disclosed in this document, it is possible to produce fine metal fine powder with good efficiency compared to the prior art rotary disk method. Gas atomization method
S -10- 201235131 和旋轉圓盤作了組合之技術（例如，非專利文獻1 )。作 爲與該些技術相異之適合製作微粉末的方法，係週知有： 對於液體金屬施加壓力，而使液體金屬從多孔質膜來分散 至相接之液體連續相中的技術（例如，專利文獻6)。 上述之粉末合成法，係均爲使熔融在氣相以及油相中 之合金粒子化的手段，所得到之粉末粒子的形狀，係爲了 使表面積成爲最小，而成爲球形。又，由於所得到之粉末 粒子的粒度分布，亦係具備有較廣之分布，因此，係有必 要因應於需要來分級爲所期望之粒度。 相對於此，在本發明中所使用之粉末合成方法，係爲 藉由將金屬粉末作爲中心核而使錫離子析出一事，來得到 粉沬的手法，粉末粒子之形狀，係並非爲球形而是成爲多 面體。又，由於粉末粒子之粒度分布亦係成爲較窄的分 布，因此，並不需要進行分級，便能夠以高良率來得到所 期望之粒度的粉末。 將金屬粉末之平均粒徑設定爲上述範圍之理由，係在 於若是超過5μιη，則在回焊時係無法得到充分之平滑性， 而若是未滿0.1 μιη，則金屬粉末之表面積係變大，用以將 被氧化了的金屬粉末表面之Sn (錫）還原所需要的助焊 劑會變多之故。 另外，在本說明書中，所謂粉末之平均粒徑，係指藉 由使用有雷射繞射散亂法之粒度分布測定裝置（堀場製作 所公司製，雷射繞射/散亂式粒子直徑分布測定裝置LA-950) 所 測定出 的體積 累積中 位直徑 （ Median 直徑： -11 - 201235131 D50)，亦即是指體積累積頻度到達] 又，本發明之預塗覆用焊錫糊， 亦即是，係含有30〜80質量％之前细 在此預塗覆用焊錫糊中，由於傍 包含有焊錫粉末，因此，能>得到回 膜以及印刷時之良好的平滑性。亦即 滿30質量％，則相對於焊錫用助焊 過少，而無法在回焊時得到必要之厚 是超過8 0 ’質量％，則相對於焊錫用 變得過多，在印刷時係無法得到良好 又，本發明之預塗覆用焊錫糊， 之金屬種互爲相異的金屬粉末之各含 焊錫粉末之全體量1〇〇質量％，係爲 亦即是，此係因爲，在預塗覆用 金屬種互爲相異的金屬粉末之各含有 錫粉末之全體量100質量％，若是未; 於一處之預塗覆焊錫，所作了混合的 成造成大的影響，起因於此，在形成 會在組成之均一性上產生問題之故。 又，本發明之預塗覆用焊錫糊， 亦即是，前述焊錫粉末，係爲多面體 亦即是，在此預塗覆用焊錫糊中 多面體，因此，粒子彼此係以面來作 粒子彼此爲作點接觸之球形粒子，在 7 5 0 %之粒徑。 係具備有下述特徵： 丨焊錫粉末。 丨以3 0〜8 0質量％而 焊時之充分厚的焊錫 是，若是焊錫粉末未 劑，焊錫@末係變得 度的焊錫膜，又，若 助焊劑，焊錫粉末係 的平滑性。 較理想，前述中心核 有比例，相對於前述 10質量％以上。 焊錫糊中，中心核之 比例，相對於前述焊 衛1 0質量％，則相對 —粉末粒子會對於組 後之預塗覆焊錫中， 係具備有下述特徵： 〇 ，由於焊錫粉末係爲 接觸，故而，相較於 印刷後以及回焊中，S -10- 201235131 and a rotating disk are combined (for example, Non-Patent Document 1). As a method suitable for producing fine powders which is different from these techniques, there are known techniques for applying a pressure to a liquid metal to disperse liquid metal from a porous film into a liquid continuous phase which is in contact (for example, a patent) Document 6). The powder synthesis method described above is a means for atomizing an alloy melted in a gas phase and an oil phase, and the shape of the obtained powder particles is spherical in order to minimize the surface area. Further, since the particle size distribution of the obtained powder particles has a wide distribution, it is necessary to classify into a desired particle size in accordance with the necessity. On the other hand, the powder synthesis method used in the present invention is a method in which tin ions are precipitated by using metal powder as a central core, and the shape of the powder particles is not spherical but Become a polyhedron. Further, since the particle size distribution of the powder particles is also a narrow distribution, it is possible to obtain a powder having a desired particle size at a high yield without performing classification. The reason why the average particle diameter of the metal powder is set to the above range is that if it exceeds 5 μm, sufficient smoothness cannot be obtained at the time of reflow, and if it is less than 0.1 μm, the surface area of the metal powder becomes large. The amount of flux required to reduce Sn (tin) on the surface of the oxidized metal powder is increased. In addition, in the present specification, the average particle diameter of the powder refers to a particle size distribution measuring device (manufactured by Horiba, Ltd., laser diffraction/scattering particle diameter distribution) by using a laser diffraction scattering method. The volume cumulative median diameter measured by the device LA-950) (Median diameter: -11 - 201235131 D50), that is, the volume cumulative frequency arrival], the pre-coating solder paste of the present invention, that is, In the solder paste for precoating which is finely contained in the range of 30 to 80% by mass, since the ruthenium contains the solder powder, good smoothness at the time of film rewinding and printing can be obtained. In other words, when the amount is 30% by mass or less, the amount of soldering for soldering is too small, and if it is not necessary to obtain a thickness of more than 80% by mass during reflow, the amount of solder is too large, and it is not good at the time of printing. Further, in the solder paste for precoating of the present invention, the total amount of each of the solder powders of the metal powders having different metal species is 1% by mass, which is because the precoating is performed. Each of the metal powders having different metal species contains 100% by mass of the tin powder, and if it is not; the pre-coating of the solder in one place causes a large influence on the mixing, and as a result, it is formed. There will be problems in the uniformity of the composition. Further, in the solder paste for precoating of the present invention, the solder powder is a polyhedron, that is, the pre-coating solder paste has a polyhedron, and therefore, the particles are surface-to-surface as particles. Spherical particles in point contact, at a particle size of 750%. It has the following characteristics: 丨 Solder powder. The solder which is sufficiently thick when soldering is 30 to 80% by mass, and if the solder powder is not used, the solder is soldered at the end of the solder, and the solder powder and the solder powder are smooth. Preferably, the central core has a ratio of 10% by mass or more with respect to the above. In the solder paste, the proportion of the center core is 10% by mass relative to the above-mentioned soldering, and the relative powder particles have the following characteristics for the pre-coated solder after the group: 〇, since the solder powder is in contact Therefore, compared to post-printing and reflow,
S -12- 201235131 係能夠維持爲剛完成印刷後之形狀。故而，藉由使用本發 明之預塗覆用焊錫糊，則由於係能夠維持於剛作了印刷後 之形狀，因此，回焊後之預塗覆用焊錫係爲薄且爲均一， 在平滑性以及對於基底金屬之表面被覆性上，係爲優良， 對於後續工程之由焊錫球之搭載等所進行的突塊形成而 言，係爲合適。進而，係亦可作爲內突塊用來作利用，不 需要經過先前技術之電鍍法或濺鍍法一般的複雜工程，便 成爲能夠形成對於基底膜之焊錫浸濕性爲優良的膜。 又，本發明之預塗覆用焊錫糊，較理想，各金屬元素 之含有比例，相對於焊錫粉末之全體量100質量％，係被 設定爲特定之範圍。 ， 亦即是，較理想，當含有銀的情況時，銀之含有比例 係爲0.1〜10質量％，當含有銅的情況時，銅之含有比例 係爲0.1〜2.0質量％，當含有鋅的情況時，鋅之含有比例 係爲0.1〜20質量％，當含有鉍的情況時，鉍之含有比例 係爲0.1〜1 0質量％，當含有鍺的情況時，鍺之含有比例 係爲0.01〜0.5質量％，當含有鎳的情況時，鎳之含有比 例係爲〇.〇1〜0.5質量％，當含有銦的情況時’銦之含有 比例係爲0.1〜10質量％，當含有鈷的情況時，鈷之含有 比例係爲〇. 1〜1 〇質量％，當含有金的情況時’金之含有 比例係爲1〜90質量％。 在此預塗覆用焊錫糊中，將上述各金屬元素之含有比 例設爲上述各範圍的理由，係在於爲了防止由於組成上與 共晶點產生大幅偏離而導致焊錫粉末之熔融溫度上升之 -13- 201235131 故。 [發明之效果] 若依據本發明，則能夠得到下述之效果 亦即是，若依據本發明之預塗覆用焊錫 心核係爲由銀、銅、鋅、鉍、鍺、鎳、銦、 單一金屬所成，而被覆層係由錫所成，因此 膜’係能夠藉由高浸濕性而得到良好的表面 性）’並且係爲薄而爲均一，在平滑性上係 後續工程之由焊錫球之搭載等所致的突塊形 合適。進而，係亦可作爲內突塊用來作利用 先前技術之電鎪法或濺鍍法一般的複雜工程 形成對於基底膜之焊錫浸濕性爲優良的膜。 故而，若是使用本發明之預塗覆用焊錫 覆焊錫’則就算是進行微節距化，亦能夠形 圖庫，並且，係能夠得到良好之焊錫接合。 【實施方式】 以下，參考圖1〜圖3，對於本發明之 糊的其中一實施形態作說明。 本實施形態之預塗覆用焊錫糊，係爲一 和焊錫用助焊劑作了混合並糊化所得到之： 糊，焊錫粉末，係如圖1中所示一般，含有 2種以上之金屬粉末，金屬粉末，係分別具 糊，則由於中 鈷或者是金之 ，相對於基底 被覆性（覆蓋 爲優良，對於 成而言，係爲 ，不需要經過 ，便成爲能夠 糊來形成預塗 成良好之焊錫 預塗覆用焊錫 種將焊錫粉末 頃塗覆用焊錫 1種、或者是 備有金屬種互 -14 - 201235131 爲相異之中心核ΙΑ、1B、和被覆中心核ΙΑ、1B之被覆 層2，且平均粒徑爲Ο.ίμιη以上5μηι以下，中心核1 a、 1B，係由銀（Ag)、銅（Cu)、鋅（Zn)、鉍（Bi)、 鍺（Ge )、鎳（Ni )、銦（In )、鈷（Co )或者是金 (Au )之單一金屬所成，被覆層2，係由錫所成.。 又，在本發明之預塗覆用焊錫糊中，係以30〜80質 量％而含有上述焊錫粉末，中心核之金屬種互爲相異的金 屬粉末之各含有比例，相對於焊錫粉末之全體量100質量 %，係分別被設爲1 〇質量％以上。 接著，針對本發明之焊錫粉末之製造方法的其中一 例，與詳細之處理程序一同作說明。首先，在溶媒中，添 加作爲錫離子而溶解了的錫化合物，並使用攪拌機，來以 較理想爲旋轉速度100〜500rpm而進行10〜30分鐘之攪 拌，藉由此而調製出包含錫離子之水溶液。.作爲溶媒，係 可列舉出水，或者是將pH調整爲0.5〜2之鹽酸水溶液、 硝酸水溶液、硫酸水溶液等。在作爲錫離子而溶解之錫化 合物中，係可列舉出氯化錫（II )、硝酸錫（II )、硫酸 錫（Π)等。 又，包含錫離子之水溶液中的錫離子之濃度，較理 想，係設爲0.05〜3莫耳/ L之範圍內。此係因爲，若是 未滿下限値，則由於錫離子之濃度係爲稀薄，因此，反應 會變得極慢’在定量性上，反應係無法結束之故。另一方 面，若是超過上限値，則由於在包含錫離子之水溶液和還 原劑水溶液之均一性混合上會耗費時間，因此，會由於反 -15- 201235131 應局部性地進行而導致粒徑成爲不均一的傾向，而並不理 想。'對於上述調製後之包含錫離子的水溶液之pH作調 整，並進而添加分散劑。爲了防止經由還原反應所析出之 金屬等的再溶解，包含錫離子之水溶液的pH，係以調整 爲0.5〜2之範圍爲理想。作爲分散劑，係可列舉出纖維 系、乙烯系之分散劑，或者是多價醇等除此之外，亦可使 用凝膠、酪蛋白、聚乙烯吡咯啶酮（PVP )等。分散劑之 添加量，較理想係爲0.001〜15質量％之範圍。在添加了 分散劑之後，更進而使用攪拌器，而以較理想爲旋轉速度 1 00〜500rpm來作1〜30分鐘之攪拌。 接著，調製出使金屬離子溶解並且使金屬微粉末作了 分散之分散液。在溶媒中，添加金屬微粉末，並使用超音 波均勻器來使其分散。構成金屬微粉末之金屬種，係爲 銀、銅、鋅、鉍、鍺、鎳、銦、鈷或者是金之金屬的任一 種。金屬微粉末之平均粒徑，係以0.1〜4μιη之範圍爲理 想。將所添加之金屬微粉末的平均粒徑設爲上述範圍之理 由，係在於，若是未滿0.1 μιη，則在錫離子之還原反應中 的核係變小，所得到之焊錫粉末的平均粒徑會低於1 μιη， 而，若是超過4μιη，則在錫離子之還原反應中的核係變 大，所得到之焊錫粉末的平均粒徑會超過5 μιη之故。 ^以使金屬微粉末之添加量和金屬離子之添加量的和’ 相對於所製造之焊錫粉末100質量％而成爲.01〜20質量％ 之範圍的方式，來添加金屬微粉末以及金屬離子。將金屬 微粉末之添加量和金屬離子之添加量的和設爲上述範圍的S -12- 201235131 can be maintained in the shape just after printing. Therefore, by using the solder paste for precoating of the present invention, since the shape can be maintained immediately after printing, the solder for precoating after reflow is thin and uniform, and smoothness is obtained. Further, it is excellent in the surface coating property of the base metal, and is suitable for the formation of a bump by mounting of a solder ball or the like in a subsequent process. Further, it can be used as an inner bump for use, and it is a film which is excellent in solder wettability to the base film without requiring complicated engineering by a plating method or a sputtering method of the prior art. In addition, the solder paste for precoating of the present invention is preferably set to a specific range with respect to 100% by mass of the total amount of the solder powder. That is, it is preferable that when silver is contained, the content ratio of silver is 0.1 to 10% by mass, and when copper is contained, the content ratio of copper is 0.1 to 2.0% by mass, when zinc is contained. In the case, the content ratio of zinc is 0.1 to 20% by mass, and when cerium is contained, the content ratio of cerium is 0.1 to 10% by mass, and when cerium is contained, the ratio of cerium is 0.01%. 0.5% by mass, when nickel is contained, the content ratio of nickel is 〇.〇1 to 0.5% by mass, and when indium is contained, the ratio of indium is 0.1 to 10% by mass, and when cobalt is contained, In the case of cobalt, the content ratio of cobalt is 〇. 1 to 1 〇 mass%, and when gold is contained, the ratio of gold content is 1 to 90% by mass. In the solder paste for precoating, the reason why the content ratio of each of the above metal elements is set to the above range is to prevent the melting temperature of the solder powder from rising due to a large deviation from the eutectic point in composition. 13- 201235131 Therefore. [Effect of the Invention] According to the present invention, it is possible to obtain the effect that the solder core core for precoating according to the present invention is silver, copper, zinc, lanthanum, cerium, nickel, indium, The single metal is formed, and the coating layer is made of tin, so the film 'is able to obtain good surface properties by high wettability' and is thin and uniform, and is smooth in subsequent engineering. A bump shape due to the mounting of a solder ball or the like is suitable. Further, it can also be used as an inner protrusion for forming a film excellent in solder wettability to a base film by a complicated process generally by the electrowinning method or the sputtering method of the prior art. Therefore, if the pre-coating solder-coated solder of the present invention is used, even if the micro-pitch is used, it is possible to form a good solder joint. [Embodiment] Hereinafter, an embodiment of the paste of the present invention will be described with reference to Figs. 1 to 3 . The solder paste for precoating of the present embodiment is obtained by mixing and gelatinizing a solder flux: paste, solder powder, as shown in Fig. 1, generally containing two or more kinds of metal powders , metal powder, each with a paste, because of the cobalt or gold, it is coated with respect to the substrate (covering is excellent, for the sake of, it is, without going through, it becomes a paste to form a good pre-coating The solder pre-coating solder type is one type of solder for solder powder coating, or a metal core -14-14 - 201235131 is a different center core 1, 1B, and a coated center core ΙΑ, 1B coating layer 2, and the average particle size is Ο.ίμιη above 5μηι, the central core 1 a, 1B, is composed of silver (Ag), copper (Cu), zinc (Zn), bismuth (Bi), bismuth (Ge), nickel ( Ni), indium (In), cobalt (Co) or a single metal of gold (Au), and the coating layer 2 is made of tin. Further, in the solder paste for precoating of the present invention, The above-mentioned solder powder is contained in an amount of 30 to 80% by mass, and the metal powder of the center core is different from each other. Each of the contents of the solder powder is set to be 1% by mass or more based on 100% by mass of the entire amount of the solder powder. Next, an example of the method for producing the solder powder of the present invention will be described together with a detailed processing procedure. First, a tin compound dissolved as tin ions is added to a solvent, and a stirrer is used to carry out stirring for 10 to 30 minutes at a desired rotational speed of 100 to 500 rpm, thereby preparing a tin ion. The aqueous solution is, for example, water, or a hydrochloric acid aqueous solution, a nitric acid aqueous solution, or a sulfuric acid aqueous solution, which has a pH of 0.5 to 2. The tin compound dissolved as a tin ion is, for example, tin chloride ( II), tin (II) nitrate, tin sulfate (Π), etc. Further, the concentration of tin ions in the aqueous solution containing tin ions is preferably in the range of 0.05 to 3 mol/L. If the lower limit is less than 値, the concentration of tin ions is thin, so the reaction becomes extremely slow. In terms of quantitative properties, the reaction system cannot be completed. On the other hand, If the upper limit is exceeded, it takes time to uniformly mix the aqueous solution containing tin ions and the aqueous solution of the reducing agent. Therefore, the reverse particle size tends to be non-uniform due to the partial progress of the reverse -15-201235131. It is not preferable. The pH of the aqueous solution containing the tin ion after the above adjustment is adjusted, and a dispersant is further added. In order to prevent redissolution of the metal or the like deposited by the reduction reaction, the pH of the aqueous solution containing the tin ion is It is preferable to adjust the range of 0.5 to 2. The dispersing agent is a fiber-based or vinyl-based dispersing agent, or a polyvalent alcohol or the like, and gel, casein, or polyethylene may be used. Pyrrolidone (PVP) and the like. The amount of the dispersant added is preferably in the range of 0.001 to 15% by mass. After the addition of the dispersant, the stirrer is further used, and stirring is preferably carried out at a rotational speed of 100 to 500 rpm for 1 to 30 minutes. Next, a dispersion which dissolves metal ions and disperses the metal fine powder is prepared. In the solvent, a metal fine powder is added and dispersed using an ultrasonic homogenizer. The metal species constituting the metal fine powder is any of silver, copper, zinc, ruthenium, iridium, nickel, indium, cobalt or a metal of gold. The average particle diameter of the metal fine powder is preferably in the range of 0.1 to 4 μm. The reason why the average particle diameter of the added metal fine powder is in the above range is that, if it is less than 0.1 μm, the nucleation in the reduction reaction of tin ions is small, and the average particle diameter of the obtained solder powder is obtained. If it exceeds 4 μm, the nucleus in the reduction reaction of tin ions becomes large, and the average particle diameter of the obtained solder powder exceeds 5 μm. The metal fine powder and the metal ions are added so that the sum of the amount of the metal fine powder and the amount of the metal ions added is in the range of 0.010 to 20% by mass based on 100% by mass of the solder powder to be produced. The sum of the amount of the metal fine powder added and the amount of the metal ion added is set to the above range
S -16- 201235131 理由，係在於，若是未滿0.01質量％，則在還原反應時之 每單位體積的核之數量係變少，所得到之焊錫粉末的平均 粒徑會超過5 μιη，而若是超過20質量％，則在還原反應 時之每單位體積的核之數量係變多，所得到之焊錫粉末的 平均粒徑會低於1 μιη，而無法得到對於焊錫粉末作粒徑控 制的效果之故。 之後，在此分散液中，使作爲由錫以外之元素所構成 的金屬離子而溶解之金屬化合物溶解。構成金屬離子之金 屬種，係爲與上述構成金屬微粉末之金屬種同一之元素， 而爲銀、銅、鋅、鉍、鍺、鎳、銦、鈷或者是金之任一 種。作爲所使用之銅化合物，係可列舉出氯化銅（II )、 硫酸銅（Π )或醋酸銅（II )等。作爲鋅化合物，係可列 舉出氯化鋅（II)、硫酸鋅（II )、硝酸鋅（II )等。作 爲鉍化合物，係可列舉出氯化鉍（III )、硫酸鉍（III ) 或硝酸鉍（III)等。作爲鍺化合物，係可列舉出氯化鍺 (II)或羧乙基鍺等。作爲鎳化合物，係可列舉出氯 化鎳（II)'硫酸鎳（II )六水物或硝酸鎳（II )六水物 等。作爲銦化合物，係可列舉出氯化銦、硝酸銦或硫酸銦 等。作爲鈷化合物，係可列舉出氯化鈷（II )、硝酸鈷 (Π )或硝酸鈷（II)等》作爲金化合物，係可列舉出四 氯化金（III)酸等。 又，以使金屬微粉末之添加量和金屬離子之添加量間 的質量比成爲1〜300之範圍的方式，來添加金屬微粉末 以及金屬離子。將金屬微粉末之添加量和金屬離子之添加 -17- 201235131 量間的比例設爲上述範圍的理由，係在於，若是上述比例 未滿1，則在還原反應時之每單位體積的核之數量係變 多，所得到之焊錫粉末的平均粒徑會低於Ιμπι，而若是上 述比例超過3 00，則在還原反應時之每單位體積的核之數 量係變少，所得到之焊錫粉末的平均粒徑會超過而 無法得到對於焊錫粉末作粒徑控制的效果之故。進而，藉 由添加分散劑，而調製出使金屬離子作了溶解之金屬微粉 末分散液。分散劑，係可使用在上述包含錫離子之水溶液 的說明中所列舉出之分散劑。分散劑之添加量，較理想， 係相對於金屬微粉末100質量％而成爲0.001〜15質量％ 之範圍。在添加了分散劑之後，更進而使用攪拌器，而以 較理想爲旋轉速度1 00〜50Orpm來作1〜30分鐘之攪拌。 接著，調製出使還原劑作了溶解的水溶液。作爲還原 劑，係可列舉出硼氫化鈉、二甲胺硼烷等之硼氫化物，聯 氨等之氮化合物、三價之鈦離子或2價鉻離子等之金屬離 子等，但是，從氧化還原反應爲可逆性而較易於作再利用 的觀點來看，係以使用2價鉻離子爲特別理想。由於2價 鉻離子係爲不安定，因此，在將此作爲還原劑的情況時， 較理想，係在將其與上述含有錫離子之水溶液以及金屬微 粉末分散液作混合的前一刻再立即作調製。 例如’只要在與包含錫離子之水溶液以及金屬微粉末 分散液作混合的前一刻，使用將三氯化鉻溶液在非氧化性 氛圍下、較理想爲在氮氣氛圍下，使其與金屬鋅作接觸並 還原爲2價鉻離子，而成爲了二氯化鉻水溶液者即可。爲S -16- 201235131 The reason is that if it is less than 0.01% by mass, the number of cores per unit volume at the time of reduction reaction is small, and the average particle diameter of the obtained solder powder exceeds 5 μm, and if When the amount is more than 20% by mass, the number of cores per unit volume at the time of the reduction reaction is increased, and the average particle diameter of the obtained solder powder is less than 1 μm, and the effect of controlling the particle size of the solder powder cannot be obtained. Therefore. Thereafter, in the dispersion, a metal compound dissolved as a metal ion composed of an element other than tin is dissolved. The metal species constituting the metal ion is the same as the metal species constituting the metal fine powder described above, and is any of silver, copper, zinc, lanthanum, cerium, nickel, indium, cobalt or gold. Examples of the copper compound to be used include copper (II) chloride, copper (Π) sulfate, and copper (II) acetate. Examples of the zinc compound include zinc (II) chloride, zinc (II) sulfate, and zinc (II) nitrate. Examples of the ruthenium compound include ruthenium (III) chloride, ruthenium (III) sulfate, and ruthenium (III) nitrate. Examples of the ruthenium compound include ruthenium (II) chloride or carboxyethyl hydrazine. Examples of the nickel compound include nickel (II) chloride's nickel sulphate (II) hexahydrate or nickel (II) nitrate hexahydrate. Examples of the indium compound include indium chloride, indium nitrate, and indium sulfate. Examples of the cobalt compound include cobalt (II) chloride, cobalt nitrate (yttrium) or cobalt (II) nitrate, and the like, and examples thereof include gold (III) chloride tetrachloride. Further, metal fine powder and metal ions are added so that the mass ratio between the amount of the metal fine powder added and the amount of metal ions added is in the range of 1 to 300. The reason why the ratio between the addition amount of the metal fine powder and the addition of the metal ions is -17-201235131 is the above range, because if the ratio is less than 1, the number of cores per unit volume at the time of the reduction reaction is When the ratio is increased, the average particle diameter of the obtained solder powder is lower than Ιμπι, and if the ratio exceeds 300, the number of cores per unit volume at the time of the reduction reaction is reduced, and the average of the obtained solder powder is obtained. The particle size may exceed the effect of controlling the particle size of the solder powder. Further, by adding a dispersant, a metal fine powder dispersion for dissolving metal ions is prepared. As the dispersant, a dispersant as exemplified in the above description of an aqueous solution containing tin ions can be used. The amount of the dispersant to be added is preferably in the range of 0.001 to 15% by mass based on 100% by mass of the metal fine powder. After the addition of the dispersing agent, the agitator is further used, and stirring is preferably carried out at a rotational speed of 100 to 50 rpm for 1 to 30 minutes. Next, an aqueous solution in which the reducing agent is dissolved is prepared. Examples of the reducing agent include a borohydride such as sodium borohydride or dimethylamine borane, a nitrogen compound such as hydrazine, a metal ion such as a trivalent titanium ion or a divalent chromium ion, and the like. From the viewpoint that the reduction reaction is reversible and is easy to reuse, it is particularly preferable to use a divalent chromium ion. Since the divalent chromium ion is unstable, it is preferable to use it as a reducing agent immediately after mixing it with the above aqueous solution containing tin ions and the metal fine powder dispersion. modulation. For example, as long as it is mixed with an aqueous solution containing tin ions and a metal fine powder dispersion, the chromium trichloride solution is used in a non-oxidizing atmosphere, preferably under a nitrogen atmosphere, to make it with metal zinc. Contact and reduce to divalent chromium ions, which can be used as an aqueous solution of chromium dichloride. for
S -18- 201235131 了防止經由還原反應所析出之金屬等的再溶解，以及防止 鉻之氫氧化物的產生，此水溶液的pH，係以調整爲與上 述所調製了的包含錫離子之水溶液同程度、亦即是0.5〜2 之範圍爲理想。 接著，將上述包含錫離子之水溶液、使金屬離子作了 溶解之金屬微粉末分散液以及還原劑水溶液作混合。首 先，將包含錫離子之水溶液和使金屬離子作了溶解之金屬 微粉末分散液，藉由靜態攪拌器等來作混合。接著，將上 述包含錫離子之水溶液和使金屬離子作了溶解之金屬微粉 末分散液的混合液，與還原劑水溶液，分別送液至反應容 器中。藉由攪拌器以及攪拌子，來將被供給至反應容器內 之包含錫離子之水溶液和使金屬離子作了溶解之金屬微粉 末分散液間的混合液、與還原劑_合液，作一定時間之攪 拌混合。此時，較理想，係以旋轉速度50〜5 OOrpm來作 5〜1 5分鐘之攪拌。 在上述攪拌混合中，係會產生錫離子之還原反應，但 是，在此還原反應時，藉由存在有由錫以外之元素所構成 的金屬離子，此金屬離子係會較錫離子而更先被還原並進 行自我核形成，在錫離子之還原反應中，錫會以該核爲中 心而成長。又，藉由在混合液中使由錫以外之元素所構成 的金屬微粉末存在，在錫離子之還原反應中，錫會將金屬 微粉末作爲核，並以該核爲中心而成長。藉由此，係能夠 得到使藉由此還原反應所析出了的粉末作了分散之分散 液。 -19 * 201235131 最後，將此分散液，藉由傾析離心機等來作 離，並將回收了的固形物，藉由將pH調整爲0.5〜 酸水溶液、硝酸水溶液、硫酸水溶液或者是甲醇、 丙酮等來作洗淨。洗淨後，再度進行固液分離，而 物回收。將從洗淨起直到固液分離爲止的工程，較 反覆進行2〜5次，之後，將回收了的固形物作 燥，藉由此，而能夠得到焊錫粉末。 藉由以上之工程，係能夠將可對應於微節距化 徑控制在平均粒徑爲1〜5μιη之範圍內的細微之 末，以較濕式還原法而更簡便之方法來以良好產率 出來。 藉由以上之工程所得到的焊錫粉末，係與焊錫 劑相混合並糊化，而成爲本實施形態之預塗覆用焊 另外，作爲上述焊錫用助焊劑，例如，係採用市面 RA (活性）或RMA (弱活性）之物。 此預塗覆用焊錫糊之調製，係藉由將焊錫用相 〜70質量％之混合來糊化一事，而進行之。亦即是 成爲含有30〜80質量％之上述焊錫粉末的方式 製。 又，中心核之金屬種互爲相異的金屬粉末之各 例，係相對於焊錫粉末之全體量1 〇〇質量％，而分 爲1 0質量％以上。 另外，在焊錫粉末中，較理想，各金屬元素之 例，相對於焊錫粉末之全體量100質量％，係被設 固液分 • 2之鹽 乙醇、 將固形 理想爲 真空乾 之將粒 焊錫粉 而製造 用助焊 錫糊。 販賣之 β作20 ，係以 來作調 含有比 別設定 含有比 定爲特S -18-201235131 Prevents re-dissolution of a metal or the like deposited by a reduction reaction, and prevents generation of a hydroxide of chromium, and the pH of the aqueous solution is adjusted to be the same as the above-described aqueous solution containing tin ions. The degree, that is, the range of 0.5 to 2 is ideal. Next, the above aqueous solution containing tin ions, a metal fine powder dispersion in which metal ions are dissolved, and an aqueous solution of a reducing agent are mixed. First, an aqueous solution containing tin ions and a metal fine powder dispersion in which metal ions are dissolved are mixed by a static stirrer or the like. Next, a mixed liquid of the above aqueous solution containing tin ions and a metal fine powder dispersion which dissolves metal ions, and a reducing agent aqueous solution are respectively supplied to the reaction vessel. By using a stirrer and a stirrer, the mixed solution of the aqueous solution containing tin ions supplied to the reaction container and the metal fine powder dispersion for dissolving the metal ions is mixed with the reducing agent for a certain period of time. Stir and mix. In this case, it is preferred to carry out the stirring at a rotation speed of 50 to 500 rpm for 5 to 15 minutes. In the above stirring and mixing, a reduction reaction of tin ions occurs, but in the case of the reduction reaction, by the presence of a metal ion composed of an element other than tin, the metal ion is more advanced than the tin ion. It is reduced and self-nucleated, and in the reduction reaction of tin ions, tin grows around the core. Further, by the presence of a metal fine powder composed of an element other than tin in the mixed solution, in the reduction reaction of tin ions, tin will grow as a core with the fine metal powder as a core. By this, it is possible to obtain a dispersion in which the powder precipitated by the reduction reaction is dispersed. -19 * 201235131 Finally, the dispersion is separated by decanting a centrifuge or the like, and the recovered solid matter is adjusted to a pH of 0.5 to an aqueous acid solution, an aqueous solution of nitric acid, an aqueous solution of sulfuric acid or methanol. Acetone and the like are washed. After washing, the solid-liquid separation is performed again, and the material is recovered. The work from the cleaning to the solid-liquid separation is repeated 2 to 5 times, and then the recovered solid matter is dried, whereby the solder powder can be obtained. With the above engineering, it is possible to control the micro-pitch diameter in the range of the average particle diameter of 1 to 5 μm, and to obtain a good yield by a simpler method than the wet reduction method. come out. The solder powder obtained by the above-mentioned work is mixed with a soldering agent and gelatinized to form a pre-coating solder of the present embodiment. Further, as the solder flux, for example, a commercially available RA (active) is used. Or RMA (weakly active). The preparation of the solder paste for precoating was carried out by mixing the solder with a phase of 70% by mass. That is, it is a system containing 30 to 80% by mass of the above solder powder. Further, each of the metal powders in which the metal cores of the center core are different from each other is 1% by mass or more based on the total amount of the solder powder. Further, in the solder powder, it is preferable that each of the metal elements is 100% by mass based on the total amount of the solder powder, and the solid solution is preferably a vacuum-dried granule solder powder. The solder paste is used for manufacturing. The sales of β is 20, which is used to adjust the content of the ratio.
S -20- 201235131 定之範圍。 亦即是，較理想，當含有銀的情況時，銀之含有比例 係爲0.1〜10質量％，當含有銅的情況時，銅之含有比例 係爲0.1〜2.0質量％，當含有鋅的情況時，鋅之含有比例 係爲0.1〜20質量％，當含有鉍的情況時，鉍之含有比例 係爲0.1〜10質量％，當含有鍺的情況時，鍺之含有比例 係爲0.01〜0.5質量％，當含有鎳的情況時，鎳之含有比 例係爲0.01〜0.5質量％，當含有銦的情況時，銦之含有 比例係爲0.1〜1 0質量％，當含有鈷的情況時，鈷之含有 比例係爲0.1〜10質量％，當含有金的情況時，金之含有 比例係爲1〜9 0質量％。 如此這般地將各金屬元素之含有比例設爲上述各範圍 的理由，係在於爲了防止由於組成上與共晶點產生大幅偏 離而導致焊錫粉末之熔融溫度上升之故。 例如，當焊錫粉末，係如圖1中所示一般，爲將以銀 作爲中心核1A之金屬的第1粉末3 A和以銅作爲中心核 1B之金屬之第2粉末3B作混合之混合粉末的情況時，係 將銀之含有比例相對於焊錫粉末之全體量1 00質量％而設 爲0.1〜1 0質量％，並將銅之含有比例相對於焊錫粉末之 全體量100質量％而設爲0.1〜2.0質量％。 接著，針對使用本實施形態之預塗覆用焊錫糊來在基 板上形成突塊的方法作說明。 首先，如圖2之（a )中所示一般，在印刷基板等之 基板4上，以將突塊附加部以外之部分作覆蓋的方式，而 -21 - 201235131 形成特定圖案之光阻5’並在使突塊附加部作了露出的基 板4上，形成銅之基底膜6。接著’如圖2之（b)中所 示一般，將突塊附加部之除了基底膜6上以外的部分（光 阻5上）藉由金屬遮罩7來作覆蓋，並使用刮刀8，來以 在基底膜6上而塡埋本實施形態之預塗覆用焊錫糊9的方 式，而進行印刷。之後’如圖2之（c )中所示一般，將 金屬遮罩7去除。接著，如圖2之（d)中所示一般，進 行回焊，而使預塗覆用焊錫糊9之焊錫粉末熔融，而在基 底膜6上形成預塗覆焊錫10。 例如，當基板4爲印刷基板的情況時，係如圖3之 (a )中所示一般，對於印刷基板所被進行安裝之外側的 .面4a和將半導體晶片1C作安裝之內側面4b的兩面，藉 由上述之方法來在突塊附加部處形成預塗覆焊錫10。 之後，如圖3之（b )中所示一般，在內側之面4b 處，係藉由金屬遮罩（省略圖示）來作覆蓋，並使用刮刀 而:印刷焊錫糊P。接著，如圖3之（C)中所示一般，藉 由進行回焊，而形成突塊15。接著，如圖4之（a)中所 示一般，將半導體晶片1C作配置，並在使半導體晶片1C 之突塊1 3與各突塊1 5作了接觸的狀態下，進行回焊，而 如圖4之（b)中所示一般，形成突塊接合部14。 之後，在外側面4a之預塗覆焊錫10處，係如圖4之 (a)中所示一般，在使例如藉由Sn-Ag-Cu所形成之焊錫 球11於預塗覆焊錫10表面上作定位並作了接觸的狀態 下，藉由進行回焊，而如圖4之（b)中所示一般，使焊S -20- 201235131 The scope of the decision. That is, it is preferable that when silver is contained, the content ratio of silver is 0.1 to 10% by mass, and when copper is contained, the content ratio of copper is 0.1 to 2.0% by mass, and when zinc is contained, When the content of zinc is 0.1 to 20% by mass, when cerium is contained, the content ratio of cerium is 0.1 to 10% by mass, and when cerium is contained, the content of cerium is 0.01 to 0.5 by mass. %, when nickel is contained, the content ratio of nickel is 0.01 to 0.5% by mass, and when indium is contained, the content ratio of indium is 0.1 to 10% by mass, and when cobalt is contained, cobalt is used. The content ratio is 0.1 to 10% by mass, and when gold is contained, the gold content ratio is 1 to 90% by mass. The reason why the content ratio of each metal element is set to the above respective ranges in this way is to prevent the melting temperature of the solder powder from rising due to a large deviation of the composition from the eutectic point. For example, when the solder powder is as shown in Fig. 1, a mixed powder of a first powder 3 A having silver as a center core 1A and a second powder 3B containing copper as a center core 1B is mixed. In the case of the total amount of the solder powder, the content of the silver is set to be 0.1 to 10% by mass based on the total amount of the solder powder, and the content ratio of the copper is set to 100% by mass based on the total amount of the solder powder. 0.1 to 2.0% by mass. Next, a method of forming a bump on a substrate using the solder paste for precoating of the present embodiment will be described. First, as shown in FIG. 2(a), generally, a photoresist pattern 5' of a specific pattern is formed on a substrate 4 such as a printed substrate by covering a portion other than the bump attaching portion. On the substrate 4 on which the bump attaching portion is exposed, a copper base film 6 is formed. Then, as shown in FIG. 2(b), the portion of the bump attaching portion other than the base film 6 (on the photoresist 5) is covered by the metal mask 7, and the doctor blade 8 is used. Printing is performed so as to embed the solder paste 9 for precoating of the present embodiment on the base film 6. Thereafter, as shown in (c) of Fig. 2, the metal mask 7 is removed. Next, as shown in (d) of Fig. 2, reflow is performed, and the solder powder of the pre-coating solder paste 9 is melted, and the pre-coated solder 10 is formed on the base film 6. For example, when the substrate 4 is a printed substrate, as shown in (a) of FIG. 3, the face 4a on the outer side to which the printed substrate is mounted and the inner side 4b on which the semiconductor wafer 1C is mounted are used. On both sides, the pre-coated solder 10 is formed at the bump attachment portion by the above method. Thereafter, as shown in Fig. 3(b), the inner surface 4b is covered with a metal mask (not shown), and a doctor blade is used to print the solder paste P. Next, as shown in (C) of Fig. 3, the bumps 15 are formed by reflow soldering. Next, as shown in (a) of FIG. 4, the semiconductor wafer 1C is placed, and the bumps 13 of the semiconductor wafer 1C are brought into contact with the respective bumps 15 to be reflowed. As shown generally in FIG. 4(b), the bump joint portion 14 is formed. Thereafter, at the pre-coated solder 10 of the outer side surface 4a, as shown in (a) of FIG. 4, the solder ball 11 formed by, for example, Sn-Ag-Cu is applied to the surface of the pre-coated solder 10. In the state of being positioned and brought into contact, by reflowing, as shown in (b) of FIG. 4, the welding is performed.
S -22- 201235131 錫球11和預塗覆焊錫10相互熔融並在基底膜6上形成突 塊1 2。 另外，上述之印刷條件以及回焊條件，例如係如同下 述一般而設定之。 使用輸送帶式回焊爐，而設爲氮氛圍且將氧濃度設爲 50〜lOOppm。又，溫度輪廓（profile )，係設爲：相對於 焊錫熔融溫度T°C，而將預熱部設爲溫度：T - 50°C〜T一 3〇°C，.將保持時間設爲30〜60秒，又，正式加熱部，係 設爲溫度：Τ+3(Γ(：〜T+50°C，將保持時間設爲30〜60 秒。 如此這般，在本實施形態之預塗覆用焊錫糊9中，中 心核，係由銀、銅、鋅、鉍、鍺、錬、銦、銘或者是金之 單一金屬所成，被覆層2，係由錫所成，並含有中心核之 金屬種爲相異之1種或2種以上之金屬粉末，所含有之金 屬粉末，係均爲將中心核藉由錫來作了被覆，相較於將由 單一金屬所成之金屬粉末直接作了添加的先前技術之焊錫 粉末，在回焊時，粉末彼此之接觸面積係成爲非常大。因 此，相較於先前技術之焊錫粉末，其之熔融性以及浸濕性 係非常良好，並且，局部性之組成偏差亦爲非常少。故 而，本實施形態之預塗覆用焊錫糊9，係能夠藉由相對於 基底膜6之高浸濕性而得到良好之表面被覆性（覆蓋 性），並且，係爲薄且爲均一，在平滑性上係爲優良，對 於由焊錫球11之搭載等所進行的突塊形成而言，係爲合 適。進而，係亦可作爲內突塊用來作利用，不需要經過先 -23- 201235131 前技術之電鍍法或濺鍍法一般的複雜工程，便成爲能夠形 成對於基底膜之焊錫浸濕性爲優良的膜。 又，由於係以30〜80質量％而包含有焊錫粉末，因 此，能夠得到回焊時之充分厚的焊錫膜以及印刷時之良好 的平滑性。 進而，中心核之金屬種互爲相異的金屬粉末之各含有 比例，係相對於焊錫粉末之全體量1 00質量％，而分別設 定爲1 〇質量％以上，藉由此，在預塗覆焊錫1 0中，係能 夠得到良好之組成均一性。 又，由於焊錫粉末係爲多面體，因此，粒子彼此係以 面來作接觸，故而，相較於粒子彼此爲作點接觸之球形粒 子，在印刷後以及回焊中，係能夠維持爲剛完成印刷後之 形狀。故而，藉由使用本實施形態之預塗覆用焊錫糊，則 由於係能夠維持於剛作了印刷後之形狀，因此，回焊後之 預塗覆用焊錫係爲薄且爲均一，在平滑性以及對於基底金 屬之表面被覆性上，.係爲優良，而成爲對於後續工程之由 焊錫球之搭載等所進行的突塊形成而言係爲合適之預塗覆 用焊錫糊。進而，係亦可作爲內突塊用來作利用，不需要 經過先前技術之電鍍法或濺鍍法一般的複雜工程，便成爲 能夠形成對於基底膜之焊錫浸濕性爲優良的膜。 [實施例] 接著，針對實際製作出上述實施形態之預塗覆用焊錫 糊的實施例、比較例之評價結果作說明。S -22- 201235131 The solder ball 11 and the pre-coated solder 10 are mutually fused and form a protrusion 12 on the base film 6. Further, the above printing conditions and reflow conditions are set, for example, as follows. A conveyor belt type reflow furnace was used, and a nitrogen atmosphere was set and the oxygen concentration was set to 50 to 100 ppm. Further, the temperature profile is set to a temperature of T - 50 ° C to T 3 ° ° C with respect to the solder melting temperature T ° C, and the holding time is set to 30. ~60 seconds, and the main heating unit is set to a temperature of Τ+3 (Γ(:~T+50°C, and the holding time is set to 30 to 60 seconds. Thus, in this embodiment, the precoating in this embodiment) In the solder paste 9, the central core is made of silver, copper, zinc, bismuth, antimony, bismuth, indium, indium or a single metal of gold. The coating layer 2 is made of tin and contains a central core. The metal species are one or more metal powders of different origins, and the metal powders contained therein are all coated with tin by a central core, and are directly made of metal powder formed from a single metal. With the addition of the prior art solder powder, the contact area of the powders with each other during reflow is very large. Therefore, compared with the solder powder of the prior art, the meltability and the wettability are very good, and, in part, The compositional deviation of the properties is also very small. Therefore, the solder paste 9 for precoating of the present embodiment is capable of Good surface coverage (covering property) is obtained by high wettability with respect to the base film 6, and is thin and uniform, and is excellent in smoothness, and is mounted on the solder ball 11 or the like. In terms of the formation of the protrusions, it is suitable. Further, it can be used as an inner protrusion, and it does not need to undergo the complicated engineering of the plating method or the sputtering method of the prior art -23-201235131. It is possible to form a film having excellent solder wettability to the base film. Since the solder powder is contained in an amount of 30 to 80% by mass, it is possible to obtain a sufficiently thick solder film during reflow and good printing. Further, the content ratio of each of the metal powders of the center nucleus is 100% by mass based on the total amount of the solder powder, and is set to 1 〇 mass% or more, whereby In the pre-coated solder 10, good composition uniformity can be obtained. Further, since the solder powder is a polyhedron, the particles are in contact with each other, so that the particles are in point contact with each other. The spherical particles can be maintained in the shape just after printing after printing and reflow. Therefore, by using the solder paste for precoating of the present embodiment, it can be maintained immediately after printing. Since the shape of the pre-coating solder after reflow is thin and uniform, it is excellent in smoothness and surface coating property to the base metal, and is used for soldering of the subsequent work. It is a suitable pre-coating solder paste for the formation of bumps, etc. Further, it can also be used as an inner bump for use without complicated engineering by prior art electroplating or sputtering. In addition, the film which is excellent in the solder wettability of the base film can be formed. [Examples] Next, the evaluation results of the examples and comparative examples of the solder paste for precoating of the above-described embodiment will be described.
S -24- 201235131 [實施例1] 首先，針對本發明之實施例的製造方法作說明。 本實施例，首先，係在水1 OOOmL中，溶解1.2mol 之氯化錫（II)，並藉由鹽酸來將pH調整爲0.2，再添加 纖維系分散劑4.5g，而設爲錫離子溶液。將平均粒徑 0.3μιη之銀粉末〇.〇84mol，在水lOOOmL中藉由超音波均 句器來作了分散，之後，在此溶液中添加纖維系分散劑 4.5g，而設爲銀微粉末分散液。 將錫離子溶液、銀微粉末分散液以及身爲還原劑之 Cr2 +分別送液至容器處，並使還原反應進行，而得到焊錫 粉末分散液。在還原反應結束後，將分散液作60分鐘之 靜置，而使焊錫粉末沈降，並將上層清澄液捨去，再於其 中加入水lOOOmL，而以300rpm來作10分鐘之攪拌，將 此操作反覆進行4次，而進行了洗淨。之後，藉由真空乾 燥機來作乾燥，並得到平均粒徑2.0μιη，銀6.0wt%之第1 粉末。 接著，將銀微粉末變更爲銅微粉末，並使用平均粒徑 〇.25 μιη之銅粉末0.02 3 mol，除此之外，藉由與銀微粉末 相同之方法，而得到了平均粒徑1.8μιη，銅l.Owt%之第2 粉末。 藉由將上述所得到之兩粉末以質量比1 : 1來作混 合，來得到相對於混合後之粉末的全體量1 00質量％而各 金屬粉末分別各包含有50質量％之焊錫粉末。在對於所' -25- 201235131 得到之焊錫粉末進行了組成分析後，其結果，錫係爲96 · 5 質量％，銀係爲3.0質量％，銅係爲〇 · 5質量％。另外，焊 錫粉末中之金屬含有量，係藉由ICP-AES(感應耦合電漿 發光分光分析裝置）來作了測定。 接著，將市面販賣之RA或RMA形態的助焊劑，和 上述焊錫粉末，以焊錫粉末：助焊劑=70質量％ : 30質 量％的_合比來作混鍊，藉由此，而製作出均具備有黏 度：約90Pa· s之預塗覆用焊錫糊。 將此些之實施例的預塗覆用焊錫糊，使用被形成有圖 案之金屬遮罩（開口徑：400μιη、厚度：20μιη)來印刷在 基板之銅上。之後，使用輸送帶爐，而在氮氛圔中進行了 最大溫度240°C之條件的回焊處理。進而，針對所形成了 的1 〇〇〇個圖案，而對於熔融性、對銅之浸濕擴廣度（表 面被覆性）、形狀以及厚度（凹凸度）作了測定。 [實施例2〜3 5、比較例1〜6 ] 關於實施例2〜35、比較例1〜6，除了設爲表1之粉 末合成條件以及表2之糊組成以外，係與實施例1同樣的 而進行了粉末合成、糊製作以及評價。針對評價結果’保 總結爲表2之糊組成以及評價結果一覽（1 )。 [實施例3 6 ] 除了使用被形成有圖案之金屬遮罩（開口徑： ΙΟΟμπι、厚度：20μπι)來印刷在基板之銅上以外，係與實S -24 - 201235131 [Embodiment 1] First, a manufacturing method of an embodiment of the present invention will be described. In this embodiment, first, 1.2 mol of tin (II) chloride is dissolved in 100 mL of water, and the pH is adjusted to 0.2 by hydrochloric acid, and then 4.5 g of a fiber-based dispersing agent is added to prepare a tin ion solution. . The silver powder having an average particle diameter of 0.3 μm was mol. 84 mol, and dispersed in a water of 1000 mL by an ultrasonic homophone. Then, 4.5 g of a fiber-based dispersing agent was added to the solution, and silver fine powder was added. Dispersions. The tin ion solution, the silver fine powder dispersion, and the Cr2 + as a reducing agent are separately supplied to the vessel, and the reduction reaction is carried out to obtain a solder powder dispersion. After the completion of the reduction reaction, the dispersion was allowed to stand for 60 minutes to allow the solder powder to settle, and the supernatant liquid was discarded, and then 100 mL of water was added thereto, and the mixture was stirred at 300 rpm for 10 minutes. It was washed four times and washed. Thereafter, it was dried by a vacuum dryer to obtain a first powder having an average particle diameter of 2.0 μm and a silver content of 6.0 wt%. Next, the silver fine powder was changed to a copper fine powder, and 0.02 3 mol of a copper powder having an average particle diameter of 2525 μιη was used, and an average particle diameter of 1.8 was obtained by the same method as that of the silver fine powder. Μιη, the second powder of copper l.Owt%. By mixing the above two powders in a mass ratio of 1:1, the total amount of the powder after mixing is 100% by mass, and each of the metal powders contains 50% by mass of solder powder. After the composition analysis of the solder powder obtained in the '-25-201235131, the tin system was 96.5% by mass, the silver system was 3.0% by mass, and the copper system was 〇·5 mass%. Further, the amount of metal in the solder powder was measured by ICP-AES (Inductively Coupled Plasma Emission Spectroscopic Analyzer). Then, the flux of the RA or RMA form sold in the market and the solder powder are mixed as a solder powder: flux = 70% by mass: 30% by mass, thereby producing a uniform It has a pre-coating solder paste with a viscosity of about 90 Pa·s. The solder paste for precoating of these examples was printed on the copper of the substrate using a metal mask (opening diameter: 400 μm, thickness: 20 μm) formed with a pattern. Thereafter, a conveyor belt furnace was used, and a reflow treatment under the condition of a maximum temperature of 240 ° C was carried out in a nitrogen atmosphere. Further, with respect to the formed one pattern, the meltability, the wetness spread to the copper (surface coating property), the shape, and the thickness (concavity and convexity) were measured. [Examples 2 to 3, Comparative Examples 1 to 6] Examples 2 to 35 and Comparative Examples 1 to 6 were the same as in Example 1 except that the powder synthesis conditions of Table 1 and the paste composition of Table 2 were used. Powder synthesis, paste production, and evaluation were carried out. The results of the evaluation are summarized as a paste composition of Table 2 and a list of evaluation results (1). [Example 3 6] In addition to using a metal mask (opening diameter: ΙΟΟμπι, thickness: 20 μm) formed with a pattern to be printed on the copper of the substrate,
S -26- 201235131 施例1同樣的而進行了粉末合成、糊製作，並進行了評 價。 本實施例，相較於實施例1，係將遮罩之開口徑設爲 1/4，而爲代表作爲內突塊用之預塗覆者。 [實施例37〜44、比較例7〜8] 關於實施例37〜44、比較例7〜8，除了設爲表1之 粉末合成條件以及表3之糊組成以外，係與實施例3 6同 樣的而進行了粉末合成、糊製作，並進行了評價。針對評 價結果，係總結爲表3之糊組成以及評價結果一覽 (2 ) 〇 [比較例9] 藉由氣體霧化法，而製作了粒徑5.0μιη之SnAgCu合 金粉末（Sn-3.0wt%Ag-0_5wt%Cu)。 接著，將市面販賣之RA或RM A形態的助焊劑，和 上述焊錫粉末，以焊錫粉末：助焊劑=70質量％: 30質 量％的混合比來作混鍊，藉由此，而製作出均具備有黏 度：約90Pa · s之預塗覆用焊錫糊。 將此些之實施例的預塗覆用焊錫糊，使用被形成有圖 案之金屬遮罩（開口徑：400μηι、厚度：20μιη )來印刷在 基板之銅上。之後，使用輸送帶爐，而在氮氛圍中進行了 最大溫度240°C之條件的回焊處理。進而，針對所形成了 的1 000個圖案，而對於熔融性、對銅之浸濕擴廣度（表 -27- 201235131 面被覆性）、形狀以及厚度（凹凸度）作了測定。 [比較例1 0 ] 藉由氣體霧化法，而製作了粒徑2.0μιη之SnAgCu合 金粉末（Sn-3.0wt%Ag-0.5wt%Cu)，除此之外，係與比 較例1 9相同的而進行了糊製作以及評價。 將糊組成以及評價結果一覽（3)總結於表4中。 關於熔融性評價，係採用佔據熔融後之焊錫表面的未 熔融焊錫之佔有面積比，並將佔有面積比爲0%以上未滿 20%的情況設爲 Good，20%以上未滿 60%的情況設爲 Fair，60%以上100%以下之情況設爲Bad。 又，關於表面被覆性，係採用佔據基底金屬表面的熔 融後之焊錫之佔有面積比，並將佔有面積比爲〇%以上未 滿70%的情況設爲Bad，70%以上未滿90%的情況設爲 Fair，90%以上100%以下之情況設爲Good。 進而，關於凹凸度，係將〇μιη以上未滿6μπΐ的情況 設爲Good，6μιη以上未滿Ιίμιη的情況設爲Fair，Ιίμηι 以上的情況設爲Bad。 另外，熔融後之焊錫表面的凹凸度之評價方法，首先 係使用雷射顯微鏡（KEYENCE公司，VK-9700 )來對於 預塗覆焊錫之3維形狀作了測定。接著，對於通過預塗覆 焊錫之中心的剖面形狀之輪廓（profile )作球面修正（將 理想球面變換爲直線之功能），並將修正後之輪廓的最高 位置和最低位置間之差作/爲凹凸度。S -26-201235131 In the same manner as in Example 1, powder synthesis and paste production were carried out and evaluated. In the present embodiment, compared with the first embodiment, the opening diameter of the mask is set to 1/4, which is representative of the pre-coater used as the inner projection. [Examples 37 to 44, and Comparative Examples 7 to 8] Examples 37 to 44 and Comparative Examples 7 to 8 were the same as Example 36 except that the powder synthesis conditions of Table 1 and the paste composition of Table 3 were used. Powder synthesis, paste production, and evaluation were carried out. The evaluation results are summarized as a paste composition of Table 3 and a list of evaluation results (2) 〇 [Comparative Example 9] SnAgCu alloy powder (Sn-3.0 wt% Ag) having a particle diameter of 5.0 μm was produced by a gas atomization method. -0_5wt% Cu). Then, the commercially available RA or RM A flux and the solder powder are mixed as a mixture of solder powder: flux = 70% by mass: 30% by mass, thereby producing a uniform It has a pre-coating solder paste with a viscosity of about 90 Pa·s. The solder paste for precoating of these examples was printed on the copper of the substrate using a metal mask (opening diameter: 400 μm, thickness: 20 μm) formed with a pattern. Thereafter, a conveyor belt furnace was used, and a reflow treatment under the condition of a maximum temperature of 240 ° C was carried out in a nitrogen atmosphere. Further, with respect to the formed 1,000 patterns, the meltability, the copper wettability (Table -27-201235131 surface coverage), the shape, and the thickness (concavity and convexity) were measured. [Comparative Example 10] A SnAgCu alloy powder (Sn-3.0 wt% Ag-0.5 wt% Cu) having a particle diameter of 2.0 μm was produced by a gas atomization method, and was the same as Comparative Example 19 except We made paste making and evaluation. The paste composition and the evaluation result list (3) are summarized in Table 4. In the evaluation of the meltability, the ratio of the area of the unmelted solder occupying the surface of the solder after melting is used, and the case where the occupied area ratio is 0% or more and less than 20% is set to be Good, and 20% or more is less than 60%. When it is set to Fair, 60% or more and 100% or less is set to Bad. Further, regarding the surface coating property, the ratio of the occupied area of the solder which occupies the surface of the base metal is used, and the case where the occupied area ratio is 〇% or more and less than 70% is Bad, and 70% or more is less than 90%. The case is set to Fair, and the case of 90% or more and 100% or less is set to Good. Further, in the case of the unevenness, the case where 〇μιη or more is less than 6 μπΐ is set to Good, and the case where 6 μm or more is less than Ιίμιη is set to Fair, and 情况ίμηι or more is set to Bad. Further, the method for evaluating the unevenness of the surface of the solder after melting was first measured using a laser microscope (KEYENCE, VK-9700) for the three-dimensional shape of the precoated solder. Next, a spherical correction is performed on the profile of the cross-sectional shape of the center of the pre-coated solder (the function of converting the ideal spherical surface into a straight line), and the difference between the highest position and the lowest position of the corrected contour is made/ Concavity.
S -28- 201235131 mi] 1 s n A g合成傕 m SnCu合成條件 S n A g粉末 1 SrtCu粉末 1 氧化錫 mm (m ο Ag 粉末酿 (mol) A g 粒徑 {μ m) 氧化錫 濃度 (mol) C u 粉末酿 (mol) Cu 粒徑 (/i m) Agig^ (w t %) 粒徑 (um) Cu誠 (w t %) 粒徑 (u m) 1 2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.7 1.0 4. 6 1.2 0.084 0. 3 1.2 0.0 2 .3 0.2 5 6.0 1.9 1.0 1.8 1.2 0,084 0. 1 1.2 0.023 0. J 6.0 0. 7 1.0 0.7 1. 2 0.035 0.5 5 — 一 一 2,5 4. 9 一 一 1. 2 0.035 0. 3 — 一 — 2.5 1.9 — — — — — 1.2 0.0 1 β 0.5 5 — — 0.7 5.0 — — — 1.2 0.016 0,2 5 — — 0.7 J . 8 1.2 0.084 0.5 5 1. 2 0.023 0.5 5 6.0 4.7 1.0 4.6 1. 2 0.084 0. 3 i. 2 0.023 0.2 5 6.0 1.9 1.0 ί. 8 1. 2 0.084 0. i 1.2 0.023 0.1 6.0 0. 7 1.0 0.7 1. 2 0.035 0.5 5 — — — 2.5 4.9 — — 1.2 0.035 0. 3 — — — 2. 5 1.9 — — — — — 1.2 0.016 0.5 5 一 1 0.7 5.0 — — — 1.2 0.016 0.2 5 =1 — 0.7 1.8 1.2 0. 0 84 0. 55 1-2 0.023 0,5 5 6.0 4.7 1.0 4.6 1.2 0. 0S4 0. 3 1.2 0.023 0. 2 5 6.0 1.9 1.0 1.8 1.2 0.084 0.1 1.2 0.023 0. Ί 6.0 0.7 1.0 0.7 ]· 2 0.035 0. 5 5 — 一 — 2.5 4.9 — — 1.2 0.035 0. 3 — — — 2.5 1.9 — — — — — 1.2 0.016 0. 5 5 —— — 0.7 5.0 — — 一 1.2 0.016 0.2 5 — 一 0.7 1.8 1.2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.8 1.0 4.7 1. 2 0.084 0. 3 1.2 0.023 0. 2 5 6.0 1.8 1.0 1.7 1.2 0.084 0.1 1.2 0.023 0.1 6.0 0. 7 1.0 0.7 1.2 0.035 0.5 5 — 一 — 2.5 4.8 — — 1-2 0.035 0. 3 一 — — 2.5 1.9 — 一 — — — I . 2 0.016 0.5 5 — — 0.7 5.0 — — — 1.2 0.016 0. 2 5 — — 0. 7 1.7 a. 2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.6 1.0 4.8 1.2 0.084 0. 3 1. 2 0.023 0. 2 5 6.0 1.9 X . 0 1 . 9 1.2 0. 0 84 0. 1 1.2 0.023 0.1 6,0 0,7 1.0 10.7 1. 2 0.035 0.5 5 _ — — 2.5 4.9 1 一 一 1.2 0.035 0. 3 — — — 2.5 1.9 — — — — — 1.2 0 ； 0 1 6 0.5 5 —— — 0.7 5. 0 — — — 】.2 0.016 0.2 5 — — 0.7 1. 8 1.2 0.0 0 6 6 0.5 5 — 一 — 0.5 0.6 — — 1.2 0.00 6 6 0.3 — 一 — 0.5 4.7 — — 1.2 0.0066 0. 1 — — — 0.5 1.9 — — 1. 2 0.0 0 6 6 0.5 5 — — — 0.5 0.6 —. 一 1.2 0.00 6 6 0.3 — — — 0. 5 4.7 — 1.2 0.0 0 6 6 0.1 — — — 0.5 1.9 — — 1.2 0.0 0 6 6 0.5 5 一 — — 0.5 0.6 — — 1.2 0.0 0 6 6 0.3 — — — 0.5 4.7 — — 1.2 0.0 0 6 6 0.1 — —— — 0.5 1.9 一 — 1.2 0.084 0.7 5 1.2 0.023 0.7 5 6.0 5. 3 1.0 5.5 α. 2 0.084 0.0 5 1.2 0, 0 2 3 0. 0 5 6.0 0-0 8 1.0 0. 0 7 1. 2 0.035 0. 7 5 — — 2.5 5.4 — — 1.2 0.035 0.0 5 — 一 一 2.5 0.0 8 — — — — — 1. 2 0.016 0.7 5 — — 0. 7 5.2 一 一 — 1.2 0.016 0. 0 5 — — 0.7 0.0 7 1.2 0.00 6 6 0.7 5 — — — 0,5 5. 5 — — 1.2 0.00 6 6 0.0 5 — — — 0.5 0. 0 8 — 一 -29- 201235131 [表2] S n A g S η C u 焊錫 粉末比 (w t %) 溶融性 表面 被覆性 凹凸度 A g (w t %) 粒徑 (ii m) cvmm (w t %) 粒徑 (/i m) 混合比 货施例] 6； 0 3.7 3 0 3.6 1/1 7 0 Good Good Fair 實施例2 6.0 1. 9 1.0 1.8 1/1 7 0 Good Good Good 實施例3 6. 0 0. 7 1.0 0.7 1/1 7 0 Good Good Good 實施例4 2.5 3.9 — — — 7 0 Good Good Fair 資施例5 2.5 1.9 — — 一 7 0 Good Good Good 實施例6 — — 0.7 4.0 — 7 0 Good Good Fair 實施例7 — 一 0. 7 1.8 — 7 0 Good Good Good 實施例8 6.0 3.7 1.0 3.6 1/1 5 0 Good Good Fair 實施例9 6.0 1.9 1.0 1.8 1/1 5 0 Good Good Good 贲施例1 0 6.0 0_ 7 1.0 0.7 1/1 5 0 Good Good Good 寊施例1 1 2.5 3. 9 — — — 5 0 Good Good Fair 賁施例1 2 2.5 1. 9 — 一 — 5 0 Good Good Good 飾例1 3 — — 0. 7 4,0 — 5 0 Good Good Fair 資施例1 4 —- — 0.7 1 8 — 5 0 Good Good Good 實施例1 5 6.0 3.7 1.0 3.6 1/1 3 0 Good Fair Good 資施例1 6 6.0 1.,9 1.0 1.8 1/1 3 0 Good F a i. r Good a施例1 7 6.0 0.7 1.0 0.7 1/1 3 0 Good Fair Good 贸施例1 8 2. 5 3. θ _ — — 3 0 Good Fair Good 實施例1 9 2.5 1.9 — — — 3 0 Good Fair Good 實施例2 0 — — 0. 7 4.0 — 30 Good Fair Good 實施例2 1 — — 0. 7 1 . 8 — 3 0 Good Fair Good 飾例2 2 6.0 3. 7 1.0 3.6 1/1 8 5 Good Fair Fair 實施例2 3 6. 0 1.9 1.0 1.8 in 8 5 Good Fair Fair 飾例2 4 6.0 0.7 1. 0 0.7 1/1 8 5 Good Fair Fair 贲施例2 5 2.5 3.9 — — —. 8 5 Q ο o d Fair Fair 寊施例2 6 2.5 1.9 — — — 8 5 Good Fair Fair 實施例2 7 一 — 0.7 4. 0 — 8 5 Good Fair Fair 實施例2 8 — — 0.7 1.8 — 8 5 Good Fair Fair 寊施例2 9 6. 0 3.7 1.0 3. 6 1/1 2 0 Good Fair Fair 寊施例3 0 6.0 1.9 1.0 1.8 1/1 2 0 Good Fair Fair 寊施例3 1 6.0 0. 7 1 ； 0 0.7 1/1 2 0 Good Fair Fair 實施例3 2 2.5 3.9 — — — 2 0 Good Fair Fair 資施例3 3 2.5 1.9 — — 一 2 0 Good Fair Fa i r ®施例3 4 — — 0. 7 4.0 — 2 0 G ο p d Fair Fair ®施例3 5 — — 0.7 1. 8 — 2 0 Good Fair Fair 比較例1 6.0 5.3 1.0 5.5 1/1 7 0 Good F a i r 〜B ad Fair 比較例2 6. 0 0.0 8 3.0 0.0 7 1/1 7 0 Bad Good Bad 比較例3 2. 5 5.4 — — — 7 0 Good F r 〜B e d Fair 比較例4 2.5 0.0 8 — — — 7 0 B a d Good Bad 比較例5 — — 0.7 5.2 — 7 0 Good F a i r〜B ad Fair 比較例6 — — 0.7 0.0 7 — 7 0 Bad Good Bad [表3] S n A g S n C υ 混合比 焊錫 粉末比 (w ίϋ) 溶融性 表面 被職 凹凸度 A g組成 (w t %) 粒徑 (w m) Cu組成 (w t %) 粒徑 (ji m) 货施例3 6 0. 5 0. 6 — — — 5 0 Good Good Fair 實施例3 7 0. 5 4. 7 — — — 5 0 Good Good Good 货施例3 8 0.5 1.9 — — —. δ 0 Good Good Good 實施例3 9 0.5 0. 6 — — — 3 0 Good Good Fair 實施例4 0 0.5 4,7 — — — 3 0 Good Good Good 货施例4 l· 0. 5 1 . 9 — — — 3 0 Good Good Good 實施例4 2 0.5 0.6 — — — 2 0 Good Fair Fair 實施例4 3 0*5 4.7 一 — — 2 0 Good Fair Fair 資施例44 0.5 1 ..9 — — — 2 0 Good F p i r Fair 比較例7 0.5 5.5 — — — 5 0 Good F a i r^-B a d Fn i r 比較例8 0.5 0.0 8 — — — 5 0 Bad Good BadS -28- 201235131 mi] 1 sn A g synthesis 傕m SnCu synthesis condition S n A g powder 1 SrtCu powder 1 tin oxide mm (m ο Ag powder (mol) A g particle size {μ m) tin oxide concentration ( Mol) C u powder (mol) Cu particle size (/im) Agig^ (wt %) particle size (um) Cu Cheng (wt %) particle size (um) 1 2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.7 1.0 4. 6 1.2 0.084 0. 3 1.2 0.0 2 .3 0.2 5 6.0 1.9 1.0 1.8 1.2 0,084 0. 1 1.2 0.023 0. J 6.0 0. 7 1.0 0.7 1. 2 0.035 0.5 5 — One 2,5 4. 9 11.1 0.035 0. 3 —1—2.5 1.9 — — — — — 1.2 0.0 1 β 0.5 5 — — 0.7 5.0 — — — 1.2 0.016 0,2 5 — — 0.7 J . 8 1.2 0.084 0.5 5 1. 2 0.023 0.5 5 6.0 4.7 1.0 4.6 1. 2 0.084 0. 3 i. 2 0.023 0.2 5 6.0 1.9 1.0 ί. 8 1. 2 0.084 0. i 1.2 0.023 0.1 6.0 0. 7 1.0 0.7 1. 2 0.035 0.5 5 — — — 2.5 4.9 — — 1.2 0.035 0. 3 — — — 2. 5 1.9 — — — — — 1.2 0.016 0.5 5 —1 0.7 5.0 — — — 1.2 0.016 0.2 5 =1 — 0.7 1.8 1.2 0. 0 84 0. 55 1-2 0.023 0,5 5 6.0 4.7 1.0 4.6 1.2 0. 0S4 0. 3 1.2 0.0 23 0. 2 5 6.0 1.9 1.0 1.8 1.2 0.084 0.1 1.2 0.023 0. Ί 6.0 0.7 1.0 0.7 ]· 2 0.035 0. 5 5 — one — 2.5 4.9 — — 1.2 0.035 0. 3 — — — 2.5 1.9 — — — — — 1.2 0.016 0. 5 5 —— — 0.7 5.0 — — A 1.2 0.016 0.2 5 — A 0.7 1.8 1.2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.8 1.0 4.7 1. 2 0.084 0. 3 1.2 0.023 0. 2 5 6.0 1.8 1.0 1.7 1.2 1.2 0.0 0.1 0.1 1.2 0.023 0.1 6.0 0. 7 1.0 0.7 1.2 0.035 0.5 5 — 1 — 2.5 4.8 — — 1-2 0.035 0. 3 ——— 2.5 1.9 — I — — — I . 2 0.016 0.5 5 — — 0.7 5.0 — — — 1.2 0.016 0. 2 5 — — 0. 7 1.7 a. 2 0.084 0.5 5 1.2 0.023 0.5 5 6.0 4.6 1.0 4.8 1.2 0.084 0. 3 1. 2 0.023 0. 2 5 6.0 1.9 X . 0 1 9 1.2 0. 0 84 0. 1 1.2 0.023 0.1 6,0 0,7 1.0 10.7 1. 2 0.035 0.5 5 _ — — 2.5 4.9 1 One to one 1.2 0.035 0. 3 — — — 2.5 1.9 — — — — — 1.2 0 ; 0 1 6 0.5 5 —— — 0.7 5. 0 — — — 】.2 0.016 0.2 5 — — 0.7 1. 8 1.2 0.0 0 6 6 0.5 5 — One — 0.5 0.6 — — 1.2 0.00 6 6 0.3 — 一 — 0.5 4.7 — — 1.2 0.0066 0. 1 — — — 0.5 1.9 — — 1. 2 0.0 0 6 6 0.5 5 — — — 0.5 0.6 —. A 1.2 0.00 6 6 0.3 — — — 0. 5 4.7 — 1.2 0.0 0 6 6 0.1 — — — 0.5 1.9 — — 1.2 0.0 0 6 6 0.5 5 ——— 0.5 0.6 — — 1.2 0.0 0 6 6 0.3 — — — 0.5 4.7 — — 1.2 0.0 0 6 6 0.1 — —— — 0.5 1.9 I — 1.2 0.084 0.7 5 1.2 0.023 0.7 5 6.0 5. 3 1.0 5.5 α. 2 0.084 0.0 5 1.2 0, 0 2 3 0. 0 5 6.0 0-0 8 1.0 0. 0 7 1. 2 0.035 0. 7 5 — — 2.5 5.4 — — 1.2 0.035 0.0 5 — 一 一 2.5 0.0 8 — — — — — 1. 2 0.016 0.7 5 — — 0. 7 5.2 One - 1.2 0.016 0. 0 5 — — 0.7 0.0 7 1.2 0.00 6 6 0.7 5 — — — 0,5 5. 5 — — 1.2 0.00 6 6 0.0 5 — — — 0.5 0. 0 8 — -29- 201235131 [Table 2] S n A g S η C u Solder powder ratio (wt %) Solubility surface coating roughness A g (wt %) Particle size (ii m) cvmm (wt %) Particle size (/im) Mix ratio example] 6; 0 3.7 3 0 3.6 1/1 7 0 Good Good Fair Example 2 6.0 1. 9 1. 0 1.8 1/1 7 0 Good Good Good Example 3 6. 0 0. 7 1.0 0.7 1/1 7 0 Good Good Good Example 4 2.5 3.9 — — — 7 0 Good Good Fair Example 5 2.5 1.9 — — One 70 Good Good Good Example 6 — — 0.7 4.0 — 7 0 Good Good Fair Example 7 — A 0. 7 1.8 — 7 0 Good Good Good Example 8 6.0 3.7 1.0 3.6 1/1 5 0 Good Good Fair Implementation Example 9 6.0 1.9 1.0 1.8 1/1 5 0 Good Good Good 1Example 1 0 6.0 0_ 7 1.0 0.7 1/1 5 0 Good Good Good 寊Example 1 1 2.5 3. 9 — — — 5 0 Good Good Fair 贲Example 1 2 2.5 1. 9 — 1 — 5 0 Good Good Good Example 1 3 — — 0. 7 4,0 — 5 0 Good Good Fair Example 1 4 —- — 0.7 1 8 — 5 0 Good Good Good Example 1 5 6.0 3.7 1.0 3.6 1/1 3 0 Good Fair Good Example 1 6 6.0 1.,9 1.0 1.8 1/1 3 0 Good F a i. r Good a Example 1 7 6.0 0.7 1.0 0.7 1/1 3 0 Good Fair Good Trade Example 1 8 2. 5 3. θ _ — — 3 0 Good Fair Good Example 1 9 2.5 1.9 — — — 3 0 Good Fair Good Example 2 0 — — 0. 7 4.0 — 30 Good Fair Good Example 2 1 — 0. 7 1 . 8 — 3 0 Good Fair Good Ornament 2 2 6.0 3. 7 1.0 3.6 1/1 8 5 Good Fair Fair Example 2 3 6. 0 1.9 1.0 1.8 in 8 5 Good Fair Fair Case 2 4 6.0 0.7 1. 0 0.7 1/1 8 5 Good Fair Fair 2 2 2 2.5 3.9 — — — 8 5 Q ο od Fair Fair 2 2 2 2.5 1.9 — — — 8 5 Good Fair Fair Example 2 7 一 — 0.7 4. 0 — 8 5 Good Fair Fair Example 2 8 — — 0.7 1.8 — 8 5 Good Fair Fair 2 2 2 6. 0 3.7 1.0 3. 6 1/1 2 0 Good Fair Fair Facilities Example 3 0 6.0 1.9 1.0 1.8 1/1 2 0 Good Fair Fair Practice 3 1 6.0 0. 7 1 ; 0 0.7 1/1 2 0 Good Fair Fair Example 3 2 2.5 3.9 — — — 2 0 Good Fair Fair Capital 3 3 2.5 1.9 — — a 2 0 Good Fair Fa ir ® Application 3 4 — — 0. 7 4.0 — 2 0 G ο pd Fair Fair ® Example 3 5 — — 0.7 1. 8 — 2 0 Good Fair Fair Comparative Example 1 6.0 5.3 1.0 5.5 1/1 7 0 Good F air ~B ad Fair Comparative Example 2 6. 0 0.0 8 3.0 0.0 7 1/1 7 0 Bad Good Bad Comparative Example 3 2. 5 5.4 — — — 7 0 Good F r ~B ed Fair Comparative Example 4 2.5 0.0 8 — — — 7 0 B ad Good Bad Comparative Example 5 — — 0.7 5.2 — 7 0 Good F air~B ad Fair Comparative Example 6 — — 0.7 0.0 7 — 7 0 Bad Good Bad [Table 3] S n A g S n C υ Mixed Ratio of solder powder (w ϋ) Surface of fusible surface A g composition (wt %) Particle size (wm) Cu composition (wt %) Particle size (ji m) Article 3 6 0. 5 0. 6 — — — 5 0 Good Good Fair Example 3 7 0. 5 4. 7 — — — 5 0 Good Good Good Example 3 8 0.5 1.9 — — —. δ 0 Good Good Good Example 3 9 0.5 0. 6 — — — 3 0 Good Good Fair Example 4 0 0.5 4,7 — — — 3 0 Good Good Good Article 4 l· 0. 5 1 . 9 — — — 3 0 Good Good Good Example 4 2 0.5 0.6 — — — 2 0 Good Fair Fair Example 4 3 0*5 4.7 One – 2 0 Good Fair Fair Example 44 0.5 1 ..9 — — — 2 0 Good F pir Fair Comparative Example 7 0.5 5.5 — — — 5 0 Good F air^-B ad Fn ir Comparative Example 8 0.5 0.0 8 — — — 5 0 Bad Good Bad
S -30 - 201235131 [表4] S η (w t %) A g (w t %) Cu (w t %) 粒徑 {μ m) 焊錫粉末比 (w t %) 溶融性 表面 被覆性 凹凸度 比較例9 9 6.5 3.0 0. 5 5. 0 7 0 Good F a i r二 Bad Bad 比較例1 0 9 6.5 3.0 0. 5 2.0 7 0 Good F a i r = Bnd~ Bad 如同由此些之結果而可得知一般，本發明之實施例， 係均具備有良好之熔融性、表面被覆性以及凹凸度。 接著，在圖5中，對於藉由SEM (掃描型電子顯微 鏡）來對本發明之實施例2的焊錫粉末作了攝影之畫像作 展示。又，在圖6中，對於亦同樣的藉由SEM來對比較 例7的焊錫粉末作了攝影之畫像作展示。如同由此些之畫 像而可得知一般，比較例之焊錫粉末，係爲球形，相對於 此，本發明之實施例的焊錫粉末，係由各種形態之多面體 所構成。 另外，本發明之技術範圍，係並不被限定於上述之實 施形態以及上述實施例，在不脫離本發明之趣旨的範圍 內，係可施加各種之變更。 [產業上之利用可能性] 本發明之預塗覆用焊錫糊，係可作爲用以進行突塊形 成或焊錫接合之預塗覆用焊錫用的焊錫糊來作利用，而可 合適地使用在細微之電子零件的安裝中。 【圖式簡單說明】 [圖1]在本發明之預塗覆用焊錫糊的其中一實施形態 -31 - 201235131 中’對於具備有互爲相異之金屬種的中心核之第1粉末以 及第2粉末作展示之槪念性剖面圖。 [圖2]在本實施形態中，對於使用有預塗覆用焊錫糊 之預塗覆焊錫的製造方法以工程順序來作展示之剖面圖。 [圖3]在本實施形態中，對於在形成有預塗覆焊錫之 散熱基板上的焊錫突塊之製造以及半導體晶片之安裝方法 以工程順序來作展示之剖面圖。 [圖4]在本實施形態中，對於在形成有預塗覆焊錫之 散熱基板上的焊錫突塊之製造以及半導體晶片之安裝方法 以工程順序來作展示之剖面圖。 [圖5]在本發明之預塗覆用焊錫糊的實施例中，對於 焊錫粉末作展示之由電子顯微鏡所得到的畫像。 [圖6]在本發明之預塗覆用焊錫糊的比較例中，對於 焊錫粉末作展示之由電子顯微鏡所得到的畫像。 【主要元件符號說明】 1A、1 B :中心核 2 :被覆層 3A :第1粉末 3B :第2粉末. -32-S -30 - 201235131 [Table 4] S η (wt %) A g (wt %) Cu (wt %) Particle size {μ m) Solder powder ratio (wt %) Fusible surface coating unevenness Comparative Example 9 9 6.5 3.0 0. 5 5. 0 7 0 Good F air two Bad Bad Comparative Example 1 0 9 6.5 3.0 0. 5 2.0 7 0 Good F air = Bnd~ Bad As can be seen from the results, the present invention In all of the examples, they have good meltability, surface coverage, and unevenness. Next, in Fig. 5, a photograph of the solder powder of Example 2 of the present invention was photographed by SEM (Scanning Electron Microscope). Further, in Fig. 6, a similar image of the solder powder of Comparative Example 7 was photographed by SEM. As is apparent from the above-described images, the solder powder of the comparative example is spherical, and the solder powder of the embodiment of the present invention is composed of polyhedrons of various forms. In addition, the technical scope of the present invention is not limited to the above-described embodiments and the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the invention. [Industrial Applicability] The solder paste for precoating of the present invention can be used as a solder paste for pre-coating solder for bump formation or solder bonding, and can be suitably used. The installation of subtle electronic parts. [Brief Description of the Drawings] [Fig. 1] In one embodiment of the pre-coating solder paste of the present invention - 31 - 201235131, the first powder and the first powder having a center core having mutually different metal species 2 The sacred profile of the powder for display. Fig. 2 is a cross-sectional view showing the manufacturing method of the pre-coated solder using the solder paste for precoating in the present embodiment. Fig. 3 is a cross-sectional view showing the manufacture of solder bumps on a heat-dissipating substrate on which pre-coated solder is formed and the method of mounting semiconductor wafers in an engineering order in the present embodiment. Fig. 4 is a cross-sectional view showing the manufacture of solder bumps on a heat-dissipating substrate on which pre-coated solder is formed and a method of mounting a semiconductor wafer in an engineering order in the present embodiment. Fig. 5 is a view showing an image obtained by an electron microscope for the solder powder in the embodiment of the solder paste for precoating of the present invention. Fig. 6 is a view showing an image obtained by an electron microscope for a solder powder in a comparative example of the solder paste for precoating of the present invention. [Explanation of main component symbols] 1A, 1 B: center core 2: coating layer 3A: first powder 3B: second powder. -32-
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| JP2011043405A JP5754582B2 (en) | 2011-02-28 | 2011-02-28 | Precoat solder paste |
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| JP (1) | JP5754582B2 (en) |
| KR (1) | KR101959084B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI460046B (en) * | 2012-11-12 | 2014-11-11 | Accurus Scient Co Ltd | High strength silver-free lead-free solder |
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| JP5971500B2 (en) * | 2012-08-13 | 2016-08-17 | 千住金属工業株式会社 | Indium ball and manufacturing method thereof |
| JP6079374B2 (en) * | 2013-03-29 | 2017-02-15 | 三菱マテリアル株式会社 | Solder powder manufacturing method and solder paste using the powder |
| JP6079375B2 (en) * | 2013-03-29 | 2017-02-15 | 三菱マテリアル株式会社 | Solder powder, method for producing the same, and solder paste using the powder |
| JP2015220396A (en) | 2014-05-20 | 2015-12-07 | 三菱マテリアル株式会社 | Method for forming solder bumps and solder paste for solder ball fixing |
| DE112014006910T5 (en) | 2014-08-28 | 2017-05-18 | E.I. Du Pont De Nemours And Company | Copper-containing conductive pastes and electrodes made therefrom |
| DE112014006903B4 (en) | 2014-08-28 | 2022-07-21 | Solar Paste, Llc | Solar cells with copper electrodes |
| US10325693B2 (en) | 2014-08-28 | 2019-06-18 | E I Du Pont De Nemours And Company | Copper-containing conductive pastes and electrodes made therefrom |
| JP6465116B2 (en) * | 2014-09-10 | 2019-02-06 | 富士電機株式会社 | Metal material, electronic component using the same, metal material manufacturing method, and electronic component manufacturing method |
| JP6587099B2 (en) * | 2015-12-15 | 2019-10-09 | 三菱マテリアル株式会社 | Solder powder, method for producing the same, and method for preparing solder paste using the powder |
| CN107877030B (en) * | 2017-11-07 | 2020-01-14 | 深圳市汉尔信电子科技有限公司 | Nano tin-bismuth composite soldering paste and preparation method thereof |
| CN114434040A (en) * | 2021-01-15 | 2022-05-06 | 重庆理工大学 | Dissimilar material interconnected zinc alloy mixed solder powder and connecting method |
| CN113231757A (en) * | 2021-06-22 | 2021-08-10 | 内蒙古玉桥合金材料制造有限公司 | Tin-based soldering paste and preparation method thereof |
Family Cites Families (18)
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| JP2784050B2 (en) * | 1989-07-12 | 1998-08-06 | 沖電気工業株式会社 | Production method of metal powder |
| JPH05154687A (en) * | 1991-11-29 | 1993-06-22 | Omron Corp | Soldering paste |
| JPH06264116A (en) | 1993-03-12 | 1994-09-20 | Electroplating Eng Of Japan Co | Production of fine metallic powder and apparatus for production thereof |
| JPH08281472A (en) | 1995-04-14 | 1996-10-29 | Senju Metal Ind Co Ltd | Solder paste for precoating |
| JPH10317022A (en) * | 1997-05-22 | 1998-12-02 | Daiken Kagaku Kogyo Kk | Production of metallic particulate powder |
| JP3335896B2 (en) * | 1997-12-26 | 2002-10-21 | 株式会社東芝 | Solder material and method for manufacturing solder material |
| DE60221872T2 (en) | 2001-10-26 | 2008-05-08 | Miyazaki Prefecture | BALL-MOLDED MONODISPERSES METAL PARTICLES |
| JP2004018956A (en) | 2002-06-17 | 2004-01-22 | Sanyo Special Steel Co Ltd | Production method for fine metal powder, and nozzle therefor |
| JP4144694B2 (en) * | 2002-11-01 | 2008-09-03 | 三井金属鉱業株式会社 | Tin-coated copper powder, method for producing the tin-coated copper powder, and conductive paste using the tin-coated copper powder |
| JP4535786B2 (en) * | 2004-06-18 | 2010-09-01 | 三井金属鉱業株式会社 | Copper-containing tin powder, mixed powder containing the copper-containing tin powder, method for producing the copper-containing tin powder, and conductive paste using the copper-containing tin powder or the mixed powder |
| JP2006225691A (en) * | 2005-02-15 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Tin-coated copper powder and electrically conductive paste using the tin-coated copper powder |
| JP2006225692A (en) * | 2005-02-15 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Tin-coated copper powder and composite electrically conductive paste using the tin-coated copper powder |
| JP2007191752A (en) * | 2006-01-18 | 2007-08-02 | Mitsui Mining & Smelting Co Ltd | Tin-coated silver powder and method for producing the tin-coated silver powder |
| JP2008138266A (en) * | 2006-12-04 | 2008-06-19 | Mitsubishi Materials Corp | Solder powder, and solder paste using the same |
| CN101234455B (en) * | 2007-01-30 | 2012-03-28 | 播磨化成株式会社 | Soldering tin paste composition and soldering-tin precoating method |
| JP4859717B2 (en) * | 2007-03-14 | 2012-01-25 | 株式会社タムラ製作所 | Solder composition |
| JP5076952B2 (en) | 2008-02-15 | 2012-11-21 | 三菱マテリアル株式会社 | Solder powder and solder paste using the powder |
| JP2010229501A (en) * | 2009-03-27 | 2010-10-14 | Mitsubishi Materials Corp | Solder powder and solder paste using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI460046B (en) * | 2012-11-12 | 2014-11-11 | Accurus Scient Co Ltd | High strength silver-free lead-free solder |
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| Publication number | Publication date |
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| KR101959084B1 (en) | 2019-03-15 |
| TWI533957B (en) | 2016-05-21 |
| CN102649201A (en) | 2012-08-29 |
| JP5754582B2 (en) | 2015-07-29 |
| CN102649201B (en) | 2016-05-04 |
| JP2012179624A (en) | 2012-09-20 |
| KR20120098513A (en) | 2012-09-05 |
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